AU2002323927B2

AU2002323927B2 - Zinc-base hot dip galvanized steel sheet excellent in retention of gloss

Info

Publication number: AU2002323927B2
Application number: AU2002323927A
Authority: AU
Inventors: Atsushi Andoh; Atsushi Komatsu; Takao Tsujimura
Original assignee: Nisshin Steel Co Ltd
Current assignee: Nippon Steel Nisshin Co Ltd
Priority date: 2002-07-24
Filing date: 2002-07-24
Publication date: 2005-08-25
Anticipated expiration: 2022-07-24
Also published as: WO2004009863A1; EP1524326A1; CA2444460C; CA2444460A1; EP1524326A4; CN1276990C; ATE484605T1; DE60238001D1; AU2002323927A1; NZ528816A; CN1503853A; ES2350921T3; EP1524326B1

Abstract

Degradation of the surface luster of a hot-dip Zn-Al-Mg plated steel sheet is inhibited by controlling the contact temperature between the plating layer and a water stream in a water cooling step after plating layer solidification, thereby suitably controlling the strip temperature during contact with the water stream, and further by incorporating a small amount of a suitable readily oxidizing element in the plating bath to stabilize the oxidation state of the plating surface layer Al and Mg. <IMAGE>

Description

SPECIFICATION

HOT-DIP ZN PLATED STEEL SHEET EXCELLENT IN LUSTER-RETAINING PROPERTY AND METHOD OF PRODUCING THE SAME TECHNICAL FIELD This invention relates to a technology for preventing surface luster degradation that sometimes occurs during production of hot-dip Zn-Al-Mg plated steel sheet using a continuous hot-dip plating line.

BACKGROUND OF THE ART JP.Hei-10-226865A, JP.Hei-10-306357A, USP No. 6,235,410 (US6,235,410 B1) and USP. No. 6,379,820 (US 6,379,820 B1) owned by the applicant of this application teach that a plated steel sheet having corrosion resistance and surface appearance sufficient to meet the requirements of an industrial product can be obtained manufacturing a hot dip Zn-base plated steel sheet using a hot-dip Zn-Al-Mg-system bath composed of Al: 4.0 Mg: 1.0- 4.0 Ti: 0.002 0.1 B: 0.001 0.045 and the balance of Zn and unavoidable impurities, and imparting to the plating layer a metallic structure including [primary crystal Al phase] and [Zn single phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure]. The production conditions for obtaining this metallic structure are set out in the published specifications.

In the course of working with such a relatively high Al- and Mg-content hot dip Zn-base plated steel sheet in ensuing production processes, the inventors experienced that, depending on the production conditions, the surface luster of the plating layer deteriorated within two to three days. This surface luster degradation of the plating layer discolors the aesthetically pleasing plated surface just after plating to a somewhat blackish interference color with passage of time (as quickly as 2 3 days but -2sometimes taking 4 7 days). The degree of outermost surface layer discoloration N(a kind of blackening) can be quantified by measuring the surface brightness. For Zexample, a plating surface that exhibited a brightness (L value) of around L 82 just 00 after manufacture degrades to around L 72 in 7 days. Although this decline in L value does not degrade the corrosion resistance property of the product and does not impair the physical and chemical qualities of the plated steel sheet, it is undesirable C from the point of surface appearance. The fact that the surface luster degradation is N not uniform over the plating surface, but takes the form of splotchy discoloration, Nparticularly detracts from the aesthetic appeal.

This degradation of surface luster can be considered to be peculiar to plated steel sheets having relatively high Al and Mg content like the hot-dip Zn-Al- Mg plated steel sheets mentioned above. The degree of oxidation of Mg concentrated in the outermost surface layer of the plating and the oxidized state of the surface layer Al are most likely complexly involved as causes of the degradation. No reports have been published to date regarding the mechanism of the surface luster degradation occurring in such a hot-dip Zn-Al-Mg plated steel sheet or regarding a method for inhibiting the degradation.

The discussion of the background to the invention herein is included to explain the context of the invention. This is not to be taken as an admission that any of the material referred to was published, known or part of the common general knowledge in Australia as at the priority date of any of the claims.

OBJECT OF THE INVENTION It would be desirable to provide means for inhibiting the degradation of surface luster that appears as a problem peculiar to hot-dip Zn-Al-Mg plated steel sheet.

DISCLOSURE OF THE INVENTION According to one aspect the present invention provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising: I I -2ao a step of continuously immersing and withdrawing steel strip Sinto/from a hot-dip Zn base bath containing Al: 4.0 15 mass and Mg: 1.0 mass thereby forming a plating layer thereon; and 00 a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating C* layer luster is inhibited at this time by controlling strip temperature on an entry side e¢3 N of said water quenching zone to lower than 105 C.

(Ni SAccording to a further aspect, the present invention provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising: a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing, in mass Al: 4.0 Mg: 1.0 Ti: 0.001 0.1%, B: 0.001 0.045%, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating layer luster is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to lower than 105'C.

According to a further aspect, the present invention provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising: a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing Al: 4.0 15 mass and Mg: 1.0 mass and added with 0.02 0.005 mass of at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si, thereby forming a plating layer thereon; and a step of thereafter continuously passing the steel strip through a water -2bo quenching zone that effects cooling while bringing the completely solidifed plating Slayer surface into contact with a water stream, wherein degradation of the plating Zlayer surface luster is inhibited at this time by controlling strip temperature on the 00 water quenching zone entry side to not lower than 105C.

(N

According to a further aspect the present invention provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising: N a step of continuously immersing and withdrawing steel strip (N into/from a hot-dip Zn base bath containing, in mass Al: 4.0- MG: 1.0 4.0 Ti: 0.001 0/1% B: 0.001 0.045%, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05%, and the balance of Zn and unavoidable impurities.

thereby forming a plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidifed plating layer surface into contact with a water stream, wherein degradation of the plating layer luster is inhibited at this time by controlling strip temperature on the water quenching zone entry side to not lower than 105C and not higher than 300'C.

According to a further aspect, the present invention provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hotdip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0- Mg: 1.0 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05%, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, which has been obtained by a process comprising: I I -2c- 0 a step of continuously immersing and withdrawing steel strip into/from N, said hot-dip plating bath, thereby forming said plating layer thereon; and a step of thereafter continuously passing the steel strip through a water 00 quenching zone that effects cooling while bringing a completely solidified surface of

(N

said plating layer into contact with a water stream, wherein degradation of a plating layer surface luster is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to not lower than 105°C.

,I According to a further aspect, the present invention provides C€3 NI a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hotdip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0- Mg: 1.0 Ti: 0.001 0.1% B: 0.001 0.045%, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05%, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, which has been obtained by a process comprising:.

a step of continuously immersing and withdrawing steel strip into/from said hot-dip plating bath, thereby forming said plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating layer surface luster is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to not lower than 105'C and not higher than 300 0

C.

According to a further aspect, the present invention provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0 Mg: 1.0 r I o at least one readily oxidizing element selected from among rare earth elements, Y, Zr Sand Si: 0.002 0.05%, and Zthe balance of Zn and unavoidable impurities, 00 thereby forming a plating layer thereon, and chemically treating the plating layer: which has been obtained by a process comprising: (,i Ca step of continuously immersing and withdrawing steel strip C€3 (Ni into/from said hot-dip plating bath, thereby forming a plating layer thereon, C€3 N a step of thereafter continuously passing the steel strip through a water quenching 10 zone that effects cooling while bringing a completely solidified surface of said (,i plating layer into contact with a water stream, wherein degradation of a plating layer surface luster is inhibited at this time by controlling strip temperature on entry side of said water quenching zone to not lower than 105 0 C, and a step of passing the steel strip passed through the water quenching zone through a chemical treatment zone.

According to a further aspect, the present invention provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0- Mg: 1.0 Ti: 0.001 0.1%, B: 0.001 0.045%, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05 and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, and chemically treating the plating layer: which has been obtained by a process comprising: a step of continuously immersing and withdrawing steel strip into/from said hot-dip plating bath, thereby forming a plating layer thereon, a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating 1 -2eo layer surface is inhibited at this time by controlling strip temperature on an entry side

C

of said water quenching zone to not lower than 105°C and not higher than 300°C, and 00 a step of passing the steel strip passed through the water quenching zone through a chemical treatment zone.

The inventors carried out extensive experimentation and research directed to overcoming the foregoing problem. As a result, we determined that the C degradation of the surface luster of hot-dip plated steel sheet is caused by the CN, reaction behavior between Q. the plating layer surface and water during water cooling in the cooling step following plating, that one way to prevent the surface luster degradation is to "control the contact temperature between the plating layer and the water stream" in the water cooling step after plating layer solidification, that, by extension, it is effective to suitably control the "strip temperature during contact with the water stream," and that it is also effective to stabilize the oxidation state of plating surface layer Al and Mg by incorporating a small amount of a suitable "readily oxidizing element" in the plating bath. By "strip temperature during contact with the water stream" is meant the strip temperature at the time cooling is conducted while forming a water film on the plating layer surface in the cooling step after completion of plating layer solidification. Specifically, it is the plating layer temperature when a water stream is passed onto the completely solidified plating layer and the plating layer is being cooled with a water film formed on the surface of the plating layer.

In other words, according to the inventors' findings, when steel strip is continuously immersed in and withdrawn from a hot-dip Zn-Al-Mg-system bath of the foregoing description and the steel strip is thereafter continuously passed through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream (while providing onto the plating layer surface an amount of water enabling momentary formation of a water film on the plating layer surface); the aforesaid degradation of plating layer surface luster can be inhibited by controlling the strip temperature on the water quenching zone entry side to lower than 105 0

C.

The strip temperature on the water quenching zone entry side, while depending on the equipment conditions, depends strongly on the sheet thickness. When the strip thickness is great, controlling the strip temperature on the water quenching zone entry side to lower than 105 'C may not be easy. It was found that in such a case, similar inhibition of surface luster degradation can be achieved without lowering the strip temperature on the water quenching zone entry side to lower than 105 'C with the temperature at 105 0 C or higher) by adding to the plating bath a small amount of an element that has a very powerful affinity for oxygen (that is a readily oxidizing element) and that has a stabilizing effect on Al oxides. Such elements include, for example, the rare earth elements, Y, Zr and Si. In actual practice, it suffices to add about 0.002 0.05 mass of the readily oxidizing element.

Thus, the present invention provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing Al: 15 mass and Mg: 1.0 4.0 mass thereby forming a plating layer thereon, and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream, degradation of the plating layer luster being inhibited at this time by controlling strip temperature on the water quenching zone entry side to lower than 105 'C.

The hot-dip Zn base bath is preferably composed of, in mass Al: 4.0 15 Mg: Ti: 0.001 0.1 B: 0.001 0.045 and the balance of Zn and unavoidable impurities.

The present invention further provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing Al: 15 mass and Mg: 1.0 4.0 mass and added with 0.002 0.05 mass of at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si, thereby forming a plating layer thereon, and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream, degradation of the plating layer surface luster being inhibited at this time by controlling strip temperature on the water quenching zone entry side to not lower than 105 'C and not higher than 300 The hot-dip Zn base bath is preferably composed of, in mass Al: 4.0 15 Mg: 1.0 4.0 Ti: 0.001 B: 0.001 0.045 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05 and the balance of Zn and unavoidable impurities.

The present invention further provides, as a hot-dip Zn plated steel sheet obtained the foregoing methods, a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0 15 and Mg: 1.0 4.0 optionally, Ti: 0.001 -0.1 %and B: 0.001 0.045 preferably, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05 and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon. The plating layer has a metallic structure including [primary crystal Al phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure] or [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure].

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a line diagram schematically illustrating a facility for producing Mg-containing hot-dip Zn plated steel sheet according to the present invention.

PREFERRED EMBODIMENTS OF THE INVENTION Generally in this specification, the term "steel strip" is used when explaining the hot-dip plating line and the term "steel sheet" is used when explaining the product. However, the steel strip and steel sheet have the same characteristics.

FIG. 1 schematically illustrates a facility used to produce a hot dip Zn-base plated steel sheet. A steel strip 2 passed through a furnace 1 to be maintained at a prescribed temperature is continuously fed into a plating bath 3. Upon exiting the plating bath 3, the steel strip passes through a wiping nozzle 4 that regulates its coating weight and then through an air-jet cooler 5. The plating layer is completely solidified during passage through the air-jet cooler 5. The strip next passes through air-water cooling zones 6a, 6b and an air cooling zone 14, any of which may be operated alone or in combination with the others, or not be operated, and then through a water quenching zone 7. It is then temperrolled in a skin pass mill 8, passed through a tension leveller 9, passed through an inspection step and taken up on a tension reel 10. When chromating or other such chemical treatment is conducted, the steel strip exiting the tension lever 9 is treated in a roll coater 11, passed through a drying zone 12 and an air cooling zone 13, and taken up on a tension reel As explained earlier, when producing a hot-dip Zn-Al-Mg plated steel sheet containing relatively large amounts of Al and Mg (hereinafter called "Mg-containing hotdip Zn plated steel sheet"), appropriate control of the cooling rate up to complete plating layer solidification and of the solidification completion position is essential from the aspect of surface property. For this, the strip feeding speed must be strictly controlled and the strip temperature at the time of passage through the air-jet cooler 5 needs to be exactly controlled in accordance with the sheet thickness. Next, so as to enable suitable temper rolling at the skin pass mill 8, the strip temperature at the skin pass entry side needs to be adjusted to a prescribed level not more than 70 by cooling conducted at the airwater cooling zones 6 (and the air cooling zone 14) and/or the water quenching zone 7.

The cooling load at these cooling zones varies with the strip running speed and the sheet thickness. Generally, water or a water solution is sprayed at the air-water cooling zones, air is jetted at the air-jet cooling zone, and, at the water quenching zone, a water stream -7adequate for momentarily forming a water film on the plating layer surface is supplied.

Compared with the first mentioned cooling stages, the latter mentioned water quenching zone can achieve a faster cooling rate owing to the contact of the water stream with the plating layer surface. Eficient cooling operation can therefore be conducted at the water quenching zone irrespective of variation in cooling load. Although water or a water solution is sprayed together with an air stream at air-water cooling zone 6, not enough water is supplied to form a water film on the plating layer surface. The cooling is therefore chiefly the result of latent heat extraction by evaporation. This is a different form of heat removal from that by contact with a water stream as in the water quenching zone and therefore differs in cooling rate.

It was found that the luster-retaining property of the plating surface differs depending on strip temperature on the water quenching zone entry side. When the temperature is 105 'C or higher, surface luster degradation readily occurs. While the reason for this is not certain, the inventors concluded that the causes involve such factors as that the reactivity of the plating layer surface is enhanced by the occurrence of a kind of boiling phenomenon when the strip temperature is 100 'C or higher upon entering the water quenching zone and that the behavior of Al under atmospheric pressure in the presence of water differs above and below about 110 AI 2 0 3

H

2 0 (or AIOOH) compound is stable above this temperature while A 2 0 3 .3H 2 0 (or AI(OH) 3 compound is stable below this temperature, so that the Al compound formed on the plating layer surface in the water quenching zone differs depending on the entry side steel strip temperature.

In an Mg-containing hot-dip Zn plated steel sheet of the foregoing type having a metallic structure including [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure], the outermost surface of the ternary eutectic crystal structure is changed into a readily oxidizing form by the aforesaid chemical reaction and this is believed to be why surface luster degradation that produces a change in brightness occurs within two or three days after plating.

-8- At any rate, the inventors discovered that, as demonstrated by the Examples set out later, the surface luster degradation of an Mg-containing hot-dip Zn plated steel sheet can be substantially prevented by regulating the temperature of the steel strip entering the water quenching zone to lower than 105 In this case, the cooling operation before entry into to the water quenching zone needs to be conducted not by supplying enough water to the completely solidified plating surface to form a water film that produces quenching, as is done in the water quenching zone, but by a mild cooling operation such as by air-water cooling (mist spraying) or air cooling air-jet cooling).

This is because regulation of the steel strip temperature entering the water quenching zone to lower than 105 'C would be meaningless if a quenching operation that forms a water film as is done in the water quenching zone should be conducted before the steel strip enters the water quenching zone. Depending on the sheet thickness and the strip running speed, the strip temperature on the water quenching zone entry side can be regulated to lower than 105 'C even by air-water cooling.

When the sheet thickness is large, however, it may sometimes be impossible to regulate the strip temperature on the water quenching zone entry side to lower than 105 Although a sufficient amount of cooling in the air-water cooling regions can be achieved even when sheet thickness is large by reducing the strip running speed, this is inadvisable because it leads to problems in solidification point control and lowers productivity. Even when the strip temperature on the water quenching zone entry side is 105 'C or higher, however, surface luster degradation can be effectively inhibited, as is demonstrated by the Examples set out later, by making present at the just completely solidified plating surface an appropriate amount of a readily oxidizing element that has a very powerful affinity for oxygen and a stabilizing effect on Al oxides, such as a rare earth element, Y, Zr or Si. In actual practice, it suffices to add about 0.002 0.05 mass of the readily oxidizing element. Although other elements that exhibit an effect similar to the rare earth elements, Y, Zr and Si may exist, none has yet been identified.

-9- These readily oxidizing elements have a property of concentrating at the outermost surface layer portion of the plating layer during the solidification process of the plating layer of the Mg-containing hot-dip Zn plated steel sheet, or even after solidification.

These elements can therefore reach a relatively high concentration at the outermost surface layer portion even when added to the plating bath in only a small amount. This is thought to enable them to inhibit surface reactions in the water quenching zone which adversely affect the surface luster-maintaining property. When these readily oxidizing elements are added to the plating bath at less than 0.002 however, they do not manifest the inhibiting effect. They must therefore be added so as to make their content in the plating bath composition not less than 0.002 mass On the other hand, amounts added in excess have poor solubility in the plating bath and even if dissolved only saturate the surface luster degradation inhibiting effect because the elements simply precipitate in excess near the grain boundaries in the plating surface layer portion. The amount added is therefore such that the content in the plating bath becomes not more than 0.10 mass in some cases not more than 0.08 mass preferably 0.05 mass more preferably 0.03 mass The surface luster degradation preventing effect produced by addition of one or more readily oxidizing elements is acts most effectively when, as explained in the foregoing, the strip temperature on the water quenching zone entry side is 105 'C or higher.

Even when the strip temperature on the water quenching zone entry side is lower than 105 however, one or more readily oxidizing elements can be added to the plating bath to stay on the safe side.

SIn the case where the strip temperature on the water quenching zone entry side is 105 'C or higher, it should preferably be controlled to not higher than 300 'C because at higher than 300 'C the cooling load in the water quenching zone becomes so large as to prevent sufficient lowering of the temperature on the skin pass entry side.

In an ordinary production line, if the strip thickness is less than 1.6 mm, the strip temperature on the water quenching zone entry side can be relatively easily made lower than 105 oC so as to ensure good luster-retaining property. When the strip thickness is 1.6 mm or greater, it is, from the aspect of actual operation, better to ensure lusterretaining property by addition of a readily oxidizing element than by forcibly cooling the steel strip so as to have a temperature on the water quenching zone entry side of lower than 105 oC.

The present invention offers a breakthrough in prevention of surface luster degradation in Mg-containing hot-dip Zn plated steel sheets and is therefore used with Mgcontaining hot-dip Zn plated steel sheets that experience surface luster degradation. Such an Mg-containing hot-dip Zn plated steel sheet is typically a hot-dip Zn-Al-Mg plated steel sheet exhibiting excellent corrosion resistance and surface appearance obtained by using a hot-dip Zn base bath composed of Al: 4.0 15% and Mg: 1.0 4.0 as basic components, plus Ti: 0.001 0.1 and B: 0.001 0.045 and the balance of Zn and unavoidable impurities, and imparting the plating layer with a metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] or [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure]. The metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] is preferably one in which the total amount of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure] [primary crystal Al phase] accounts for not less than 80 vol. of the metallic structure, more preferably for not less than 95 vol. thereof. The balance can consist of [Zn phase] and [Zn 2 Mg phase], plus, in some cases, small amounts of [Zn/Zn 2 Mg binary eutectic crystal] and/or [Al/Zn 2 Mg binary eutectic crystal]. When Si is added, small amounts of [Si phase], [Mg 2 Si phase], [Al/Mg 2 Si binary eutectic crystal] and the like may also be present.

The present invention thus provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hotdip plating bath comprising, in mass Al: 4.0- 15 -11- Mg: 1.0 4.0 Ti: 0.001 -0.1% B: 0.001 0.045 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05 and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon. The plating layer has a metallic structure including [primary crystal Al phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure] or [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure]. It has a structural characteristic in the point that the one or more readily oxidizing elements are concentrated in the outermost surface layer portion of the plating layer.

The addition amounts, actions and effects of the Al, Mg, Ti, B etc. making up the plating bath remain the same in the plating bath added with at least one readily oxidizing element in accordance with the present invention. Addition of Ti and B is beneficial because these elements act to inhibit generation and growth of Zn, ,Mg 2 phase that has and adverse effect on appearance and corrosion resistance when the plating layer is given the aforesaid metallic structure including a Zn 2 Mg ternary eutectic crystal structure.

To obtain this effect by adding Ti, B, or Ti-B alloy or compound to the bath, it suffices to make the addition so that the content in the bath becomes Ti: 0.001 0.1 and B: 0.001 0.045 At higher contents than these, precipitates grow in the plating layer to produce "bumps" (called as "butsu" in Japanese language) in the plating layer that detract from the surface appearance.

Al present in the plating layer improves the corrosion resistance of the :plated steel sheet and operates to inhibit dross generation during plated steel sheet production. When the Al content is less than 1.0 mass the corrosion resistance improving effect is insufficient and the effect of inhibiting generation of Mg oxide system dross is also low. The Al content is preferably made not less than 4.0 mass On the other -12hand, when the Al content exceeds 15 mass pronounced growth of an Fe-AI alloy layer at the interface between the plating layer and the base steel sheet degrades plating adherence. The Al content is preferably 4.5 13.0 mass more preferably 5.0 10.0 mass and most preferably 5.0 7.0 mass Mg present in the plating layer generates a uniform corrosion product on the plating layer surface and, by this, operates to markedly enhance the corrosion resistance of the plated steel sheet. When the Mg content is less than 1.0 this action of uniformly generating such a corrosion product is insufficient. On the other hand, when the Mg content exceeds 4.0 the corrosion resistance improvement effect by Mg saturates and generation of undesirable Mg oxide system dross occurs more readily. The Mg content is therefore defined as 1.0 4.0 mass%. The Mg content is preferably 1.5 4.0 mass more preferably 2.0 3.5 mass most preferably 2.5 3.5 mass It was found that the aforesaid surface luster degradation problem also occurs when chemical treatment is applied at the final stage of the Mg-containing hot-dip Zn plated steel sheet production line such as by using the roll coater 11 shown at the bottom of FIG. 1, irrespective of whether a chromate coating, a chromate-free conversion coating, an' organic resin film containing chromium acid, or a silicate film containing chromium acid or other such film is formed. Depending on the production conditions, the phenomenon of a decline in brightness and surface luster degradation after a few days also occurs (or does not occur) in a plated product having a film produced by chemical treatment, just as it does (or does not) when chemical treatment is not conducted. It was found that this problem can be similarly overcome by controlling the aforesaid strip temperature on the water quenching zone entry side and adding at least one readily oxidizing element to the plating bath in accordance with the present invention.

S More specifically, also in the case where the steel strip is passed through a chemical treatment zone after being passed through the water quenching zone, the surface luster degradation of the chemically treated Mg-containing hot-dip Zn plated steel sheet 1111w_ -13can be inhibited by, as in the foregoing method of producing an Mg-containing hot-dip Zn plated steel sheet, controlling the strip temperature on the water quenching zone entry side to lower than 105 'C or adding 0.002 0.05 mass of a readily oxidizing element to the plating bath.

The present invention thus provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hotdip plating bath comprising, in mass Al: 4.0- 15 Mg: 1.0 4.0 Ti: 0.001 -0.1 B: 0.001 -0.045 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 -0.05 and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, and chemically treating the plating layer.

Example 1 A hot-dip Zn base bath containing about 6 mass of Al, about 3 mass of Mg, about 0.05 mass of Ti and about 0.01 mass of B in zinc was constituted in a facility like that shown in FIG. 1 and an Mg-containing hot-dip Zn plated steel sheets (thickness: 0.8 1.0 mm) were manufactured to have a plating layer with a metallic structure including of [primary crystal Al phase], [Zn phase] and [Zn2Mg phase] in a matrix of [AI/Zn/Zn 2 Mg ternary eutectic crystal structure]. At this time, the strip temperature on the outlet side of the air-jet cooler 5 was made 335 'C or lower so as to complete solidification of the plating layer in the cooler, the cooling conditions and strip running speed were made substantially constant in the air-water cooling zones 6a, 6b, the -14air cooling zone 14 and the water quenching zone 7, the strip temperature on the water quenching zone 7 entry side was made 100 °C or lower, and the steel strip was passed through the skin pass mill at about 70 'C or lower. The surface luster of the Mg-containing hot-dip Zn plated steel sheet obtained was excellent and no phenomenon causing degradation thereof was observed.

Steel strips of 1.6 mm or greater thickness were passed under substantially the same conditions as those set out above. Although strip temperature on the water quenching zone 7 entry side rose to around 120 150 the operation itself was trouble free and Mg-containing hot-dip Zn plated steel sheets having the same excellent surface luster were produced. After two or three days, however, the surface luster of these steel sheets declined slightly, with the brightness L value of some being observed to decrease from 82 just after manufacture to around 75 two days later. The cooling capacity of the airwater cooling zones 6a, 6b was then increased to drop the strip temperature on the water quenching zone 7 entry side to lower than 105 As a result, the surface luster degrading phenonienon was no longer observed.

Also when chromating treatment was conducted, whether or not surface luster degradation occurred again depended on the strip temperature on the water quenching zone 7 entry side. From this it was learned that surface degradation occurs when chromating treatment is conducted in the same way as when it is not.

Example 2 Building on the experience acquired in the preceding Example, the degree of plating layer surface luster degradation was investigated by conducting tests under various conditions. The surface luster was assessed as the brightness measured as the Lab method L value using a spectrophotometer.

First, during production of hot-dip Zn-Al-Mg plated steel sheets under the "Plating conditions" set out below, air-water cooling (mist spraying) and water quenching (water stream projection) were conducted under the "Cooling conditions" set out below from the strip temperature at completion of plating layer solidification to about 30 The degrees of surface luster degradation of test pieces taken from the obtained plated steel sheets were evaluated by measuring their L values once just after plating and again after a constant temperature and humidity test in which the test pieces were held in a thermohygrostat maintained at a temperature of 60 "C and a relative humidity of 90 for hours starting from just after plating.

Plating conditions Processed steel strip: Hot-rolled steel strip of 2.0 mm thickness Plating bath composition: Al 9.0 mass Mg 2.3 mass Balance Zn Plating bath temperature: 430 "C Coating weight: 90 g/m 2 Strip running speed: 80 m/min Cooling conditions Air-water cooling Nozzle: Two-fluid nozzle Fluids: Water (pressure 12.5 kPa) Air (pressure 4.0 kPa) Mist water flow: As shown in Table 1 Mist airflow: As shown in Table 1 Average mist particle diameter: About 50 Im Strip temperature at start of mist spraying: As shown in Table 1 Strip temperature at end of mist spraying: As shown in Table 1 Water quenching Water stream projector: 7 header rows each consisting of 10 flat spray nozzles spaced at 150 mm intervals in the direction of strip width Fluid: Water (pressure 2.5 kgf/cm 2 Water flow: As shown in Table 1 -16- Strip temperature at start of water stream projection: As shown in Table 1 Strip temperature at end of water stream projection: As shown in Table 1 The L values of plated steel sheets obtained under the foregoing conditions at different strip temperatures at start of stream projection (strip temperature on the water quenching entry side) measured just after plating and after the 20-hour constant temperature and humidity test are shown in Table 1. The metallic structures of the plating layers were examined by microscopically observing a cross-section of the plating layer of each plated steel sheet. The plating layer of every steel sheet had a metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure], sometimes further including [Zn phase] and [Zn 2 Mg phase] (hereinafter called "Zn 2 Mg-system" metallic structure).

-17- Table 1 Plating bath composition: Al 9.0 mass Mg 2.3 mass Balance: Zn No. Cooling conditions Surface luster Air-water cooling Water quenchin_ L value L value after 20-h Example Mist water Mist Strip temperature Strip temperature Water Strip temperature at start Strip temperature j ust afe constant ter 2 mpeera flow airflow at start of mist at end of mist flow of water stream at end of water jus after constant temperature type spraying spraying projection stream projection plating and humidity test m 3 /h m 3 /min °C OC m 3 /h 0C A-I 10 1000 198 131 150 92 30 82 82 Invention A-2 10 1000 280 207 150 101 30 82 81 Invention A-3 8 600 280 223 150 112 30 82 74 Comparative A-4 4 600 280 245 150 132 31 81 70 Comparative -18- As can be seen from the results in Table 1, when the strip temperature on the water quenching entry side was higher than 105 OC, the tendency for the brightness L value to decrease became stronger as the temperature increased. In contrast, when the temperature was lower than 105 the brightness just after plating was retained without change over the course of time, demonstrating that Mg-containing hot-dip Zn plated steel sheets exhibiting excellent luster-retaining property were obtained.

Example 3 Mg-containing hot-dip Zn plated steel sheets produced under the following conditions using the same cooling conditions after plating layer solidification as in Example 2 were examined for state of surface luster degradation. The results are shown in Table 2.

Plating conditions Processed steel strip: Hot-rolled steel strip of 3.2 mm thickness Plating bath composition: Al 6.3 mass Mg 3.2 mass Ti 0.008 mass B 0.002 mass Balance Zn Plating bath temperature: 390 'C Coating weight: 120 g/m 2 Strip rumiing speed: Varied as shown in Table 2 Cooling conditions Gas cooling (Cooling with air-jet cooler only) Nozzle: Plate-like nozzle with slit of 5 mm width Gas: Air (pressure 4 kPa) Airflow: As shown in Table 2 Strip temperature at start of air cooling: As shown in Table 2 Strip temperature at end of air cooling: As shown in Table 2 Water quenching -19- Water stream projector: 7 header rows each consisting of 10 flat spray nozzles spaced at 150 mm intervals in the direction of strip width Fluid: Water (pressure 2.2 kgf/cm 2 Water flow: As shown in Table 2 Strip temperature at start of water stream projection: As shown in Table 2 Strip temperature at end of water stream projection: As shown in Table 2 Table 2 Plating bath composition: Al 6.3 mass 3.2 mass Ti: 0.008 mass B 0.002 mass Balance: Zn Cooling conditions Surface luster Air cooling ___Water quenching_______ No. Strip run- ng L value L value after 20-h Example ning speed Airflow Strip temperature Strip temperature Water Strip temperature at start Strip temperature ju aer cstant temp e at start of cooling at end of cooling flow of water stream at end of water j ust after constant temperature type projection stream projection plating and humidity test m m in n oc oC m'/h oC °C B-I 23 0 120 82 30 81 81 Invention B-2 31 2500 167 126 120 82 30 81 81 Invention B-3 40 2500 185 140 120 102 30 81 80 Invention B-4 40 1200 185 158 120 118 30 81 73 Comparative 56 2500 212 164 120 131 31 81 71 Comparative -21 As can be seen from the results in Table 2, in this Example as in Example 2, when the strip temperature on the water quenching entry side was higher than 105 "C, the tendency for the brightness L value to decrease became stronger as the temperature increased, but when the temperature was lower than 105 the brightness just after plating remained the same even after the 20-hour constant temperature and humidity test.

The metallic structures of the plating layers were examined by microscopically observing a cross-section of the plating layer of each plated steel sheet. A "Zn 2 Mg-system" metallic structure was consistently obtained in every steel sheet.

Example 4 Nos. B-2 to B-5 of Example 3 were subjected to chemical treatment of their water-quenched plating surfaces under the conditions set out below. Their brightnesses just after chemical treatment and after a 20-hour constant temperature and humidity test were measured by the method of Example 2. The results are shown in Table 3.

Chemical treatment conditions A Application method: Spray and wringer roll method Processing solution: Zinchrome 3387N from Nihon Parkerizing Co., Ltd. (solution total chromium concentration: 10 g/L) Chromium coating weight: 10 mg/m 2 Chemical treatment conditions B Application method: Roll coating method Processing solution: Zinchrome 3387N added with 1 g/L of zirconium fluoride (solution total chromium concentration: 20 g/L) Chromium coating weight: 40 mg/m 2 Chemical treatment conditions C Application method: Roll coating method -22- Processing solution: Aqueous solution composed mainly of 50 g/L of magnesium phosphate, 10 g/L of potassium fluorotitanate and 3 g/L of organic acid Metallic component coating weight: 50 mg/m 2 Chemical treatment conditions D Coating formed by the following two-step processing Bottom layer Application method: Shower and wringer roll method Processing solution: Zinchrome 3387N (solution total chromium concentration: 10 g/L) Chromium coating weight: 10 mg/m 2 Top layer Application method: Roll coating method Organic coating: Urethane resin (thickness: 1.5 Lm) Table 3 Chemically Chemical Surface luster Example treated treatment L value just after L value after 20-h constant Type plating layer conditions chemical treatment temperature and humidity test No. B-2 A 81 81 Invention No. B-4 A 81 72 Comparative No. B-3 B 81 80 Invention No. B-5 B 81 70 Comparative No. B-3 C 81 81 Invention No. B-4 C 81 73 Comparative No. B-2 D 81 81 Invention No. B-5 D 81 72 Comparative As can be seen from the results in Table 3, when the strip temperature on the water quenching entry side was 105 °C or higher, the brightness value L decreased with passage of time irrespective of the chemical treatment applied. When the temperature was lower than 105 the brightness just after plating was retained without change.

-23- Example Plating was conducted under the following plating conditions and cooling conditions with one or more readily oxidizing elements added to the plating bath. Each plating was examined for surface luster degradation. The results are shown in Table 4.

Plating conditions Processed steel strip: Hot-rolled steel strip of 1.6 mm thickness Plating bath composition: As shown in Table 4 Plating bath temperature: 450 °C Coating weight: 190 g/m 2 Strip running speed: 60-120 m/min Cooling conditions Air-water cooling Nozzle: Two-fluid nozzle Fluids: Water (pressure 1.0 3.5 kgf/cm 2 Air (pressure 2.5 5.0 kgf/cm 2 Mist water flow: 0 8 m'/h Mist airflow: 0 600 m'/min Average mist particle diameter: 10 30 pm Gas cooling Nozzle: Plate-like nozzle with slit of 5 mm width Gas: Air (pressure 4 kPa) Airflow: 0 3500 m'/m Water quenching Water stream projector: 7 header rows each consisting of 10 flat spray nozzles spaced at 150 mm intervals in the direction of strip width Fluid: Water (pressure 3.0 kgf/cm 2 Water flow: 180 m'/h Strip temperature at start of water stream projection: As shown in Table 4 24- Table 4 Plating bath coposition (mass balance Zn) Strip temperature on the water Chemical Surface luster Example No. Al Mg T, B Readily oxidizing element quenching entry side treatment L value just after L value after 20-h type Type Content 0 C plating or chemical constant temperature humidity C-i 13.8 2.2 0.046 0.020 Y 0.030 198 No 81 80 Invention C-2 8.2 2.9 0.012 0.005 Y 0.009 96 No 82 82 Invention C-3 9.4 3.3 0.009 0.010 La 0.007 155 No 82 81 Invention Ce 0.010 C-4 4.5 1.3 0.037 0.038 Zr 0.028 237 No 81 80 Invention 6.1 3.3 0.024 0.009 Zr 0.003 131 No 82 81 Invention C-6 10.3 3.7 0.005 0.006 Zr 0.029 103 No 82 82 Invention C-7 7.8 3.2 0.011 0.002 Si 0.041 138 No 82 82 Invention C-8 6.3 3.0 0.050 0.003 Si 0.023 100 No 82 82 Invention C-9 5.2 2.6 0.008 0.004 Si 0.004 83 No 82 82 Invention 5.6 2.5 0.006 0.001 Zr 0.001 146 No 81 72 Comparative C-11 11.5 2.0 0.073 0.015 La 0.001 174 No 81 66 Cmparative C-12 6.1 3.3 0.024 0.009 Zr 0.003 131 Yes (Type B) 82 81 Invention C-13 13.8 2.2 0.046 0.020 Y 0.030 198 Yes (Type C) 81 80 Invention C-14 6.3 3.0 0.050 0.003 Si 0.023 100 Yes (Type C) 82 82 Invention 5.6 2.5 0.006 0.001 Zr 0.001 146 Yes (Type B) 81 73 Comparative C-16 4.4 1.8 Zr 0.021 109 No 82 82 Invention C-17 6.3 2.9 Y 0.005 145 No 82 82 Invention 0.012 C-18 5.7 3.2 Si 0.02N8 167 Yes (Type B) 181 81 Inveto As shown in FIG. 4, when plated steel sheets like those whose brightness values L fell to around 71 after the 20-hour constant temperature and humidity test in Examples 2 and 3 were produced in the same manner except for the addition of at least one readily oxidizing element to the plating bath, the decline in brightness L value was inhibited by the added readily oxidizing element. When the plating surface layer portion of the No. C-7 Mg-containing hot-dip Zn plated steel sheet added with Si was subjected to analysis of its elemental composition by ESCA, it was found that almost all of the Si was concentrated in the outermost surface layer portion of the plating and almost no Si was present in the interior of the plating layer.

A comparison of the ESCA analysis results for a plated steel sheet whose brightness L value decreased during the 20-hour constant temperature and humidity test (No. Cwith the results for a plated steel sheet whose brightness L value did not decrease (No. C-5) showed that Mg tended to be heavily present in the outermost surface layer portion of the plating layer of the former plated steel sheet.

Table 4 includes cases in which the water-quenched plating layer was chemically treated (No. C-12 to No. C-15). The degree of decline in brightness L value differs depending on whether or not a readily oxidizing element is added and it can be seen that a readily oxidizing element was added, decrease in brightness L value was inhibited.

As explained in the foregoing, the present invention can effectively prevent the phenomenon of surface luster degradation that is peculiar to Mgcontaining hot-dip Zn plated steel sheets. It is therefore capable of providing Mgcontaining hot-dip Zn plated steel sheet that is good in corrosion resistance and also excellent in luster-retaining property.

Throughout the description and claims of this specification, the word "comprise" and variations of that word, such as "comprising" and "comprises" are not intended to exclude other additives, steps or integers.

Claims

2. A method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising: a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing, in mass Al: 4.0 Mg: 1.0 Ti: 0.001 0.1%, B: 0.001 0.045%, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating layer luster is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to lower than 105 0 C. -27-
3. A method of producing a hot-dip Zn plated steel sheet excellent in luster- retaining property comprising: a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing Al: 4.0 15 mass and Mg: 1.0 4.0 mass and added with 0.002 0.05 mass of at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si, thereby forming a plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream, wherein degradation of the plating layer surface luster being inhibited at this time by controlling strip temperature on the water quenching zone entry side to not lower than 105 'C.
4. A method of producing a hot-dip Zn plated steel sheet excellent in luster- retaining property comprising: a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing, in mass Al: 4.0- 15 Mg: 1.0 4.0 Ti: 0.001 -0.1 B: 0.001 0.045 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05 and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream, wherein degradation of the plating layer luster I 1 is inhibited at this time by controlling strip temperature on the water quenching zone entry side to not lower than 105 C and not higher than 300'C. 00
5. A method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property according to any of claims 1 to 4, further C* comprising a step of passing the steel strip passed through the water quenching Ci zone through a chemical treatment zone.
6. A hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0 Mg: 1.0 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05%, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, which has been obtained by a process comprising: a step of continuously immersing and withdrawing steel strip into/from said hot-dip plating bath, thereby forming said plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating layer surface luster is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to not lower than 105 0 C.
7. A hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0- I SMg: 1.0 ZTi: 0.001 0.1% 00 B: 0.001 0.045%, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05%, and C* the balance of Zn and unavoidable impurities, ~thereby forming a plating layer thereon, N which has been obtained by a process comprising: a step of continuously immersing and withdrawing steel strip into/from said hot-dip plating bath, thereby forming said plating layer thereon; and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating layer surface luster is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to not lower than 105'C and not higher than 300 0 C.
8. A hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0 Mg: 1.0 at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05%, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, and chemically treating the plating layer: which has been obtained by a process comprising: a step of continuously immersing and withdrawing steel strip into/from said hot-dip plating bath, thereby forming a plating layer thereon, a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said 00 plating layer into contact with a water stream, wherein degradation of a plating layer (N surface luster is inhibited at this time by controlling strip temperature on entry side of said water quenching zone to not lower than 105'C, and a step of passing the steel strip passed through the water quenching N zone through a chemical treatment zone. e¢3
9. A hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass Al: 4.0 Mg: 1.0 Ti: 0.001 0.1%, B: 0.001 0.045%, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 0.05 and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, and chemically treating the plating layer: which has been obtained by a process comprising: a step of continuously immersing and withdrawing steel strip into/from said hot-dip plating bath, thereby forming a plating layer thereon, a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing a completely solidified surface of said plating layer into contact with a water stream, wherein degradation of a plating layer surface is inhibited at this time by controlling strip temperature on an entry side of said water quenching zone to not lower than 105 0 C and not higher than 300'C, and a step of passing the steel strip passed through the water quenching zone through a chemical treatment zone. I I A method of producing a hot-dip Zn plated steel sheet substantially as herein described with reference to Figure 1 or any one of Examples 1 00 5, excluding the Comparative Examples.
11. A hot-dip Zn plated steel sheet obtained by hot-dip plating a steel strip using a hot-dip plating bath, substantially as herein described with reference to CN Figure 1 or any one of Examples 1 5, excluding the comparative examples. DATED: 25 July, 2005 PHILLIPS ORMONDE FITZPATRICK Attorneys for: Nisshin Steel Company, Ltd. Qeu~fi~k1