WO2006035527A1

WO2006035527A1 - HIGHLY CORROSION RESISTANT Zn ALLOY PLATED STEEL MATERIAL HAVING HAIRLINE APPEARANCE

Info

Publication number: WO2006035527A1
Application number: PCT/JP2005/006975
Authority: WO
Inventors: Akira Takahashi; Yoshio Kimata; Satoru Tanaka
Original assignee: Nippon Steel Corporation
Priority date: 2004-09-28
Filing date: 2005-04-04
Publication date: 2006-04-06
Also published as: CN101027422A; JP2006124824A; JP4546848B2; KR20070042578A; CN101027422B; KR100881777B1

Abstract

A highly corrosion resistant zinc alloy plated steel material having a hairline appearance that can find application in the same usages as those of stainless steel material. There is provided a highly corrosion resistant Zn alloy plated steel material with a hairline appearance, having hairlines formed on a surface layer of plating layer of 10 to 600 g/m2 plated skin quantity composed of 1 to 60 mass% Al, 0.1 to 10 mass% Mg and the balance of Zn and unavoidable impurities, which hairlines are characterized in that in the direction perpendicular to the hairlines, the surface roughness Ra is in the range of 0.2 to 2.5 μm and the peak count PPI in the range of 50 to 400; along the hairline direction, the surface roughness Ra is in the range of 0.1 to 1.2 μm and the peak count PPI in the range of 1 to 100; the surface roughness Ra in the direction perpendicular to the hairlines is ≥ 1.2 times the surface roughness Ra along the hairline direction; and the PPI in the direction perpendicular to the hairlines is ≥ 2.0 times the PPI along the hairline direction.

Description

Description High-corrosion-resistant steel with a hairline appearance

The present invention relates to a highly corrosion-resistant Zn-based alloy-plated steel material having a hairline appearance that is used for interior materials such as buildings and vehicles, exterior materials, and surface layers of electrical equipment. Background art

Stainless steel is well known as a steel material having a conventional hairline appearance. In other words, hairline finish (HL finish) is specified in JISG 4 3 0 5 and 4 3 0 7 as one of the surface finishes of stainless steel materials, and hair line finishes are “continuous with abrasives of appropriate grain size” This means that the polished surface is long and continuous like hair, as defined as “polished and finished so that it has a polished surface”.

Figure 1 shows an overview of hairline finishing. As shown in Fig. 1, the usual hair finishing method is to use an endless paper polishing belt 3 that spans the contact wheel 1 and the handle 2 and the contact wheel. It is well known that this is a processing method of polishing the surface of a stainless steel material 6 that is rotated at a high speed by rotating and moving from the uncoiler 4 to the coiler 5 with a polishing belt (for example, Japanese Patent Laid-Open No. 1-3 0 6 1 6 And Japanese Patent Publication No. 7-9 6 1 8 3). Stainless steel with a hairline finish is corrosion resistant and has a unique surface pattern, so it is widely used for interior materials for exterior materials and exterior materials for electrical equipment, where design is important. However, since stainless steel is expensive, a new inexpensive material that replaces stainless steel has high corrosion resistance similar to stainless steel, and has a hairline appearance suitable for use in building materials and electrical equipment. desired.

Therefore, the present inventor paid attention to a zinc-plated steel material that has excellent corrosion resistance and is inexpensive as well as a stainless steel material, and studied to apply a hairline finish thereto.

The conventional technology for applying a hairline finish to a plating layer is to form a plating coating layer on the surface of a thin and light magnesium-based member, and then form a hairline pattern on the surface of the plating coating layer by a hairline finish. In this case, a technique has been proposed that solves the problem that the base of the plating coating layer comes out and the corrosion resistance deteriorates, and a stable and high quality member cannot be obtained.

That is, a glazing coating layer selected from Cu, Cu alloy, Au, Au alloy, Al, A1 alloy formed on the surface of Mg-based parts by the dry soldering method (1 ), And Cu, Ni, Au, Cr, Zn, Pa, Pt, Rh, F formed on the plating coating layer (1) by a wet plating method. This is a technique for applying a hairline finish to the surface of an Mg-based part having a plating coating layer (2) selected from e, Co, Sn, Cd, Ru, and alloys thereof (for example, JP-A 2 0 0 0—See 2 1 9 9 7 gazette). However, this technique requires a double thick plating coating layer, and it is necessary to combine the dry plating method with the wet plating method. It is difficult to adapt it to steel.

In addition, various inventions have been made for high corrosion resistance Zn-based alloy-plated steel sheets. For example, a Zn-A1-Mg alloy-plated steel sheet has a mass of ⁰ /. A 1: 3 to 17%, Mg: 1 to 5%, remaining Z n force 2005/006975 Plated steel sheet using a bath, or a plated steel sheet using a plating bath to which Ti or B is added (see, for example, Japanese Patent Laid-open No. Hei 10-300 637), or , Z n— A 1 — M g— S i alloy-plated steel sheet, in mass%, A 1: 5 to 8%, M g: 1 to 10%, S i: 0.0 1 to 2 %, If necessary, Fe: 1% or less, or further, a plated steel sheet having a plating layer containing Sn: 0.1-2% is known (for example, Japanese Patent Laid-Open No. 0 1— 3 5 5 0 5 3). Disclosure of the invention

An object of the present invention is to provide a highly corrosion-resistant zinc-based alloy-plated steel material having a hairline appearance that can be similarly applied to the same use as that of a stainless steel material having a hairline appearance.

The present inventor has eagerly studied hairline finishing on a zinc-plated steel material, which is a material cheaper than stainless steel material and having similar corrosion resistance as a material to replace a stainless steel material having a hairline appearance. As a result, when a hairline finish is applied to a pure zinc-plated steel material, zinc is soft, so the formed hairline can be easily pickled, and the hairline finish polishing belt is easily clogged during processing. The hairline could not be obtained, and the hairline finishing was difficult. In addition, galvanized steel with a hairline finish has white rust on the surface of the zinc in the atmosphere, and the appearance of the hairline disappears when the white rust is generated, eliminating the effect of forming the hairline. wait.

Therefore, in the present invention, when focusing on the high corrosion resistance Zn-based alloy plating including a hard phase in the adhesion layer, and applying a hairline finish to this, a high corrosion resistance zinc plated steel material having a good hairline appearance is obtained. As a result, the present invention was completed. The gist of the present invention is as follows.

(1) Metsusa adherence is 10 ~ 60 0 g Zm ² and A 1 is 1 ~ 6

0% by mass, Mg is contained in an amount of 0.1 to 10% by mass, and the balance has a hairline formed on the surface layer of the plating it made of Zn and inevitable impurities. The surface roughness R a in the perpendicular direction is 0.2 to

2.5 μm, peak number PPI is 50 to 400, surface roughness Ra in hairline direction is 0.1 to 1 • 2 μm, peak number PPI force is: L The surface roughness Ra in the direction perpendicular to the hairline is 1 • 2 times the surface roughness Ra in the hairline direction, and the PPI in the direction perpendicular to the hairline is 2.0 of the PPI in the hairline direction. High corrosion-resistant zinc alloy galvanized steel with hairline appearance, characterized by being more than double.

(2) Amount of adhesion is 10 to 6 000 g Zm ² and A 1 is 1 to 6

Contains 0 to 10% by weight, Mg 0.1 to 10% by weight, with the balance being the hairline formed on the surface of the plating layer consisting of Zn and inevitable impurities

The hairline has the number of peaks perpendicular to the hairline; P P I force S 50

~ 4 00, number of peaks in the hairline direction PPI force S 1 ~: 1 0 0, and PPI in the direction perpendicular to the hairline is more than 2.0 times PPI in the hairline direction High corrosion resistance zn alloy galvanized steel with hair appearance.

(3) The amount of plating is 10 to 60,000 g "m ² , 1 to 60% by mass of A 1, 0.1 to 10% by mass of Mg, the balance being Zn and inevitable Hairline formed on the surface of the plating layer consisting of mechanical impurities

The hairline has a surface roughness Ra in the angular direction of the hairline of 0.1.

~ 2.5 μm, number of peaks P P I is 50 to 400, surface roughness R in hairline direction is 0, 1 to 1.2 β m, number of peaks P P I force S 1 ~: 10

The surface roughness R a in the direction perpendicular to the hairline is 0 and more than 1. times the surface roughness Ra in the hairline direction, and the PPI in the direction perpendicular to the hairline is 5006975 A highly corrosion-resistant zinc-based alloy-plated steel material having a hairline appearance characterized by being 2.0 times or more the PPI in the hairline direction.

(4) The plated layer further contains 3 1 in an amount of 0.001 to 3% by mass. The hair appearance according to any one of (1) to (3) High corrosion resistance Zn-based alloy steel.

(5) The plating layer further contains one or two of T i from 0.001 to 0.1% by mass and B from 0.000 to 0.1% by mass. (1) to (4) characterized in that the high-corrosion-resistant Zn-based alloy-plated steel material having the hairline appearance.

(6) The plating layer has a volume ratio of 1 to 80 V o 1% for the binary eutectic of Zn and A 1, and a volume ratio of 1 for the ternary eutectic of the Zn, A 1 and Zn Mg alloy. 0 ~ 90 V o 1%, the total of both is 50% or more

(1) to (5) A high corrosion resistance Zn-based alloy steel with a hairline appearance according to any one of (1) to (5).

(7) on the plating layer surface, high corrosion resistance Z n having a hairline appearance Ki载in any one of and having chromate treatment layer ^{l~ 1 0 0 0 mg Zm 2} (1) to (6) Steel alloy steel.

(8) The surface of the plating layer has a chromium-free treatment layer that does not contain chromium in an amount of 1 to 20 ◦ mg Zm ² (1) to

(6) A highly corrosion-resistant zinc-based alloy-plated steel material having the hairline appearance described in any one of (6).

(9) A high corrosion resistance Z having a hairline appearance according to any one of (1) to (8), characterized by having a transparent resin film layer having a thickness of 0.5 to 100 m on the surface. n-base alloy steel.

(10) Co, Fe, Ni, Pt: One or more metal states of Mn or water in the vicinity of the interface between the plating layer surface and the chromate-free treatment layer containing no chromium Oxide deposit layer is 0.1 ~ The high corrosion resistance Zn-based alloy having the hairline appearance according to any one of (1) to (9), characterized by having 10 mg / m ² and excellent blackening resistance in a humid environment Metal steel. Brief Description of Drawings

Figure 1 shows an overview of hairline finishing.

Fig. 2 is a diagram showing the structure of the Zn-based alloy plating layer of the present invention. (A) is a photomicrograph of the Zn-based alloy plating layer of the present invention, and (b) is a schematic diagram of the structure. It is.

Fig. 3 shows high corrosion resistance Zn alloy steel with a hairline finish (Zn— 1 1% A 1 — 3 Mg — 0. 2 Si plating, plating basis weight: 90 g / m ² ) Is a cross-sectional photomicrograph (magnification: 100000 times) of the surface after polishing # 80.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

Steel materials with a hairline appearance include stainless steel materials with a hairline finish, but stainless steel materials are expensive. Therefore, the present inventors paid attention to a zinc-based plated steel material having high corrosion resistance as in the case of stainless steel materials, and researched on applying a hairline finish to the zinc-based plated steel material.

When a pure galvanized steel material was finished with a hairline, the hairline peaked and the hairline was crushed, and a hairline with a good appearance could not be obtained, and some bare metal was exposed. In addition, there was a problem that the polishing belt for hairline finishing was clogged, and further, there was a problem that white rust was generated when it was left in the air after hairline finishing, and the appearance of the hairline disappeared. The reason why such a good hairline cannot be obtained is thought to be due to the fact that the zinc plating layer is soft with a hardness of about 5 OHv. Therefore, paying attention to the zinc alloy-based adhesive layer containing a hard phase and applying a hairline finish to this, a good hairline with an excellent appearance could be obtained. The zinc alloy-based plating layer containing a hard layer is a zinc alloy-based plating layer containing Al and Mg, which is a binary eutectic of Z n and A 1 and Z It has been found that a plating layer containing n, A 1 and a ternary eutectic hard layer of a ZnMg alloy is suitable. The component of the plating layer is ⁰ / mass. A 1: 1.0 to 60%, Mg: 0.1 to 10%, balance Zn and unavoidable impurities, and for the purpose of improving corrosion resistance. 0 0 1 to 3.0%, for the purpose of improving the appearance T i: 0. 0 0 0 1 to 0.1%, B: 0. 0 0 0 1 to 0.1% 1 type or 2 types It may be selected and contained as necessary.

The reason for limiting the components of the zinc alloy-based adhesive layer will be described.

A 1, together form a ternary eutectic of Z n / two yuan eutectic of A 1 and _{Z n ZA 1 / Z n 2} M g of the hard phase in plated layer, improve the corrosion resistance of the plated layer In addition, it has the effect of suppressing dross generation in the plating bath.

If A 1 is less than 1.0%, the volume occupancy of the binary eutectic and ternary eutectic, which is a hard phase, is insufficient, and a good hairline with an excellent appearance cannot be obtained with a hairline finish. The corrosion resistance of the plated steel material is inferior. On the other hand, when A 1 exceeds 60%, sink-like depressions occur on the surface of the mating surface, and the appearance cannot be made uniform, and the effect of improving the corrosion resistance is saturated and at the same time the sacrificial anticorrosive action against the base iron is achieved. Disappears, and the corrosion resistance of the buttock deteriorates. Therefore, the content of 1 is set to 1.0 to 60%.

Mg is a component necessary to form a ternary eutectic and It has the effect of forming corrosion products on the surface and improving the corrosion resistance of the steel. If Mg is less than 0.1%, the occupancy rate of the ternary eutectic is insufficient, and a good hairline with an excellent appearance cannot be obtained with a hairline finish, and corrosion generation is necessary to improve corrosion resistance. Things cannot be formed. On the other hand, if Mg exceeds 10%, oxidation of the bathing bath proceeds due to contact with the atmosphere to produce black oxide (dross), making it difficult to squeeze and saturate the effect of improving corrosion resistance. . Therefore, the Mg content was set to 0.1 to: 10%.

Si is added as necessary to improve corrosion resistance and plating adhesion. If the added amount is less than 0.001%, these effects cannot be obtained.If the added amount exceeds 3.0%, these effects are saturated, and instead dross generation increases. ◦ ◦ 1 to 3. ◦%.

T i is a component added as necessary to generate primary A 1 phase precipitation nuclei, refine the structure and improve the appearance, and it is necessary to add 0.001% or more. is there. However, if added over 0.1%, the solubility in the plating bath will be exceeded, and Ti 1 A 1 -based precipitates will grow, resulting in irregularities on the surface of the plating layer and deterioration in appearance quality. 1 was set to 0.0% 0 to 0.1%.

B has the effect of improving the appearance of the eye as T i .However, the effect cannot be obtained if it is less than 0.001%, and the effect is saturated if it exceeds 0.1%. , B was set to 0.0 0 ◦ 1 to ◦. 1%.

The coating weight is less than 10 g'Zm ² because it is inferior in corrosion resistance, and if it is 600 gZm ² or more, the uniform adhesion of the plating layer deteriorates and the appearance of sagging is not preferable. Cracking of the adhesion layer due to processing, etc. is likely to occur. Therefore, Fig. 2 (a) with an upper limit of 600 g Zm ² is a photomicrograph of the structure of the Zn-based alloy plating layer of the present invention, Figure 2 (b) is a schematic diagram of the organization.

As shown in Fig. 2 (b), for example, the cross-sectional structure of the highly corrosion-resistant Zn-based alloy layer consisting of Zn— 1 1% A 1 _ 3% Mg — 0.2% S i is [Z n / A 1 / Z n ₂ M g] ternary eutectic phase 7 is mixed with [Z n / A 1] binary eutectic phase 8 and [Z n ₂ Mg Single phase] 9 is an island-like structure.

This ternary eutectic phase has a structure in which soft Zn and A 1 phases and hard Zn ₂ Mg are mixed and dispersed, and the entire structure has both stickiness and hardness. Show properties. If a steel plate with such a phase is also present on the surface, the plating surface is easily peeled off from the plating surface by the abrasive belt without causing a sag in the hairline peak. A beautiful hairline can be obtained, and a good hairline with excellent appearance can be obtained without clogging the polishing belt.

Fig. 3 shows the high corrosion resistance Zn-based alloy steel with a hairline finish (Zn— 1 1% A 1 — 3 M g— 0.2 S i plating, plating basis weight: 90 g / m ² ) is a cross-sectional photomicrograph (magnification: 100000 times) of the surface after polishing # 80. As shown in Fig. 3, it has a good appearance without sagging in the groove of the hairline.

In order to obtain a hairline with an excellent appearance by applying a hairline finish to a steel material with high corrosion resistance and Zn alloy, [Zn / A1] binary eutectic phase occupies the volume as the structure of the plating layer At a rate :! ~ 8 0 vo 1%, [ Z n / A 1 / Z n 2 M g] Sangentomo phase is present 1% 1 0~ 9 0 V o in volume occupancy, the remainder Z n, Z n ₂ M g alloy, M g ₂ S i, is preferably a structure consisting T i a l ₃ like. [ZnZAl] The binary eutectic phase is softer than the ternary eutectic phase, but harder than the Zn and A1 single phase. Therefore, the smaller the volume occupancy, the more the hairline treatment Improves. If it is 90 V o 1% or more, the entire plating layer becomes soft and the hairline property is inferior, and it is difficult to engineering to 1 V 0 1% or less. When the volume ratio of the ternary eutectic decreases, the hardness and stickiness characteristics of the plating layer decrease, the appearance during hairline treatment deteriorates, and clogging of the abrasive due to debris tends to occur. Therefore, the lower limit of the volume occupancy of the ternary eutectic was set to 10 V 0 1%. On the other hand, the upper limit was that the A 1 phase and Zn ₂ Mg phase were likely to occur during the solidification process of the plating layer, and 90 vo 1% was the upper limit in engineering production. In addition, if the volume fraction of the eutectic phase combined with both decreases, the hardness and viscosity of the entire plating layer decrease and the appearance of the hairline becomes poor.

The thickness of the plating layer suitable for performing the hairline finish is in the range of 10 to 600 g / m ² , preferably 10 to 500 g / m ² . If the adhesion amount is less than 10 g / m ² , the adhesion layer is too thin, resulting in insufficient corrosion resistance and exposing the steel substrate with a hairline finish. If the coating weight exceeds 600 g / m ² , the plating layer will become too thick to make the plating layer uniform in appearance, and the plating layer will be easy to peel off. Further, it is not preferable. Therefore, the coating weight and 1 0~ 6 0 0 g Z m 2.

As a hairline shape with excellent appearance formed on steel steel, the surface roughness in the direction perpendicular to the hairline (C direction) is surface roughness: a: 0.2 to 2.5 μπι, preferably Is 1.2 to 1.8 μΐη and the number of peaks is Ρ Ρ I: 50 to 400, and the surface roughness in the hairline direction (L direction) is a: 0.1 to 1.2 / m, preferably Is 0.5 to 1. Ο μ πι and the number of peaks Ρ Ρ 1 is 1 to 100, and R a in the direction perpendicular to the hairline (C direction) is in the hairline direction (L direction); 1. More than 2 times (C direction: a / L direction: a ≥ 1.2) and hairline perpendicular direction (C direction The PPI in the direction is preferably at least twice the PPI in the hairline direction (L direction) (C direction PPI / L direction PPI ≥ 2).

If the surface roughness Ra in the C direction and the L direction specified in these, the number of peaks P P I and the ratio thereof are less than the lower limit, the hairline becomes inconspicuous and the hairline finish is wasted. On the other hand, the surface roughness Ra in the C direction and the L direction, the number of peaks: If the upper limit of the PPI value is exceeded, the hairline becomes too rough, and it is not a beautiful hairline but a design as a hairline. The product value is lost.

Therefore, in the present invention, the shape of the hairline is defined by the surface roughness, the number of peaks, and the ratio thereof as described above. The surface roughness Ra was measured by adopting a reference length of 0.8 mm in accordance with the measurement method defined in JISB 060 (199). The peak number PPI (P eaks Per Inch) is 1 inch according to the regulations of S AE J 9 1 1 — 1 9 8 6 and the width 2 H between the positive and negative reference levels is 5 0 μ inch. And measured.

In order to form a hairline that satisfies the requirements of surface roughness, number of peaks, and their ratio as defined in the present invention, hairline finishing is performed using a belt sander (abrasive belt) of # 60 to # 320. It is preferable to carry out.

After the hairline finish, it is preferable to perform a primary anti-bacterial treatment by applying a chromate treatment or a chromate-free treatment to the plating layer.

Since zinc-plated steel tends to generate white glaze, the anti-glare coating layer can be formed by applying a chromate treatment or a chromate-free treatment after the hairline finish is applied to the plating layer. The primary defense process to form In the case of chromate treatment, it is possible to apply a known chromate treatment, for example, a chromate treatment with a chromate treatment solution containing chromic acid and a reaction accelerator as main components. can be a click Rome preparative adhesion amount with 1~2 OO mg Zm ^2.

If the amount of chromate is less than 1 mg / m ² , a sufficient anti-mold effect will not be obtained, and if it exceeds 200 mg / m ² , not only will the hairline finish be inconspicuous, The effect is saturated and the cost is increased economically.

Similarly to the chromate process, the primary defense process can also be performed by a known chromate free process (non-chromate process).

Chromate-free treatment (non-chromate treatment) does not contain environmentally harmful hexavalent cucumber in the treatment solution. For example, treatment solution containing Zr, Ti salt, etc. There is a treatment liquid containing a pipetting agent, and a chrome free treatment using a known chrome free treatment liquid can be applied. In these chromate-free treatments, a chromate-free treatment layer that does not contain chromium, mainly composed of Ti, Zr, P, Ce, Si, A1, Li, etc., is formed. The adhesion amount is preferably 1 to 100 O mg Zm ² .

Click Lome one xanthohumol Lee deposition amount of processing can not be obtained sufficient Bo鲭effect is less than lmg / m ^2, also becomes inconspicuous § La Lee down finish to 1 0 0 O mg / m ² by weight, Not only that, but the anti-fouling effect is saturated, resulting in high costs.

In addition, if a zinc-lined steel material is subjected to a hairline finish and left in the atmosphere, the plating surface will oxidize and turn black. If the color changes to black (black), the hairline finish becomes inconspicuous and the appearance of the hairline is impaired. In addition, the zinc plating layer tends to wrinkle when it collides with a hard object. For this reason, the plated surface with the hairline finish is transparent. If the bright resin coating layer is formed to a thickness of 0.5 to 100 m, the blackening resistance and the scratch resistance can be improved. The transparent resin coating layer can be formed by a conventionally known coating method using a conventionally known organic clear paint. Specific examples of such organic clear paints include acrylic-based baking clear paints, urethane-based clear paints, epoxy-based clear paints, and polyester-based clear paints. Paints, melamine alkyd clear paints, and the like. Of these, polyester-based and acrylic-based clear paints are preferably used.

Specific examples of the coating method of the organic clear paint include a roll coater method, a curtain coater method, a spray gun method, and an electrostatic method. Among these, the roll coater method and the curtain coater method are preferable.

In order to improve blackening resistance, one or more metal states or hydroxylation of Co, Fe, Ni, Pt, and Mn are used in the vicinity of the interface with the chromate or chromate-free treatment layer. It is advisable to apply a physical deposit layer. This deposit layer has a good adhesion amount of 0.1 to 1 O mg Zm ² , preferably 0.5 to ^3. O mg Zm ² . This treatment greatly improves the resistance to blackening in a humid environment. The effect of blackening resistance is at a coverage is 0. lmg Zm ² or less is not sufficient, 1 0 mg Zm ² or more, the corrosion resistance of the deterioration caused undesirable. The method for applying the treatment layer is not particularly limited, but examples include an immersion method of the salt aqueous solution, a spray method, and a vacuum deposition method. In the dipping method, a steel plate with a hairline treatment is immersed in the metal salt aqueous solution of 0.1 to 1 ° g / L for 0.5 to 10 seconds and then washed with water.

Example

Hereinafter, the present invention will be described in detail based on examples.

Two types of low-carbon steel with thicknesses of 0.8 mm and 1.6 mm The plate was used as a blank plate.

Plating was performed by heating, annealing, and plating in a non-oxidizing furnace type continuous molten zinc plating line. The annealing atmosphere encloses an atmosphere of 10% hydrogen and the remaining 90% nitrogen gas, with a dew point of 130 ° C. The annealing temperature is 7 30 ° C and the annealing time is 3 minutes. The composition of the plating bath is, by mass, A1: 11.0%, Mg: 3.0%, Si: 0.2%, the balance Zn and inevitable impurities, and the plating bath temperature is The temperature was 45 ° C. The coating amount was adjusted by the usual nitrogen gas wiping method.

After plating, hairline finishing was performed using a belt sander with different count (size 100 mm x 9 15 mm) at a belt speed of about 3.5 Z seconds and a polishing time of 3 to 4 seconds. Thereafter, the surface roughness (R a) and the number of peaks (P P I) were examined.

The results are shown in Table 1.

As shown in Table 1, No. 1, 2 and 5 satisfy the conditions of surface roughness (R a), peak number (PPI) and their ratio defined in the present invention. It became a steel material with high corrosion resistance and a good hairline appearance.

On the other hand, No. 3 subjected to # 80 bead blast treatment had uniform fine irregularities formed on the surface, but the surface roughness in the L direction and the number of peaks were small, and The ratio of the surface roughness and the number of peaks was small and did not satisfy the requirements specified in the present invention, and the bead blasting and hairline finishing were clearly different.

No. 4 was finished with a hairline, but the belt sander was too rough as # 600 and did not meet the hairline requirements stipulated in the present invention. I could not observe. No. 6 and No. 7 are cases where the hairline finish was not performed, but in this case, the surface roughness in the C direction and the number of peaks were small. And their ratio was small. Of course, no hairline was observed in this case.

From the above test results, only a steel plate with a hairline finish that satisfies the requirements specified in the present invention was a plated steel plate having a beautiful hairline appearance.

Next, galvanized steel sheets with various coating layer compositions were prepared, and after plating, using a belt sander with size # 80 (size 100 mm x 9 15 mm), the belt speed was about 3. Hairline finishing was performed under conditions of 5 Z seconds and polishing time of 3 to 4 seconds. At that time, we investigated the appearance of the hairline and the state of adhesion of debris.

The results are shown in Table 2. Nos. 1 to 17 had the squeezing composition defined in the present invention, and were good results in any of hairline appearance, sander glaze, and corrosion resistance. On the other hand, No. 18 to 20 are platings other than the composition specified in the present invention, and the surface roughness value satisfies the value specified in the present invention, but the appearance of the hairline cannot be clearly observed. The generation of freckle and corrosion resistance were poor. The reason why the appearance of the hairline could not be clearly observed is thought to be due to the generation of debris and the soaking of the polishing wrinkles. .

In addition, plating with varying volume occupancy of the eutectic phase in the plating layer was created and its performance was investigated. The results are shown in Table 3. No .:! To 5 had a phase structure defined in the present invention, and were good results in both hairline appearance and sander haze, that is, corrosion resistance. On the other hand, Nos. 6 and 7 are platings other than the phase structure defined in the present invention, and the appearance of hairline was inferior and the generation of flaws was poor.

Furthermore, chromate treatment, chromate-free treatment, clear coating treatment, and blackening resistance treatment were performed using a steel plate with a composition of Z n _ ll A l — 3 Mg _ 0.2 Si. It was. The chromate treatment is chromic acid 1 After applying the 0 g / 1 solution, it was dried for 30 seconds in a hot air oven at 60 ° C. In the chromate-free treatment, a chemical agent consisting of ammonium zirconium carbonate, cobalt nitrate, silica, and ammonium phosphate was applied and then dried in a hot air oven at 60 ° C. for 30 seconds. In addition, apply melamine alkyd clear paint (solvent type) and acryl type clear paint (water dispersion type) at 220 ° C (melamine alkyd type) and 15 50 The plate was heated to a plate temperature of ° C (Atalyl type). The blackening resistance treatment was immersed in an aqueous solution of lg ZL in sulfuric acid Ni for 3 seconds, then washed with water and dried, and then applied with the above chrome-free treatment and melamine alkyd clear coating. The evaluation of the corrosion resistance on the flat surface was determined by the amount of white mist generated after 2400 hours of salt water fog test of JISZ 2 3 3 1, ◯: White mist generated 1% or less, and X: 10% or more. The cross cut portion was evaluated by a blister width after 100 hours of the salt spray test, and judged as follows: ○: less than 2 mm, X: 2 mm or more. The blackening resistance was evaluated by allowing the treated steel to stand in a high-temperature and high-humidity tank at 60 ° C. and a relative humidity of 85% for 7 days, and evaluating the color difference δ E value between before and after standing. The color difference δ Ε was measured according to JISZ 8 7 2 2. When δE is 1 or less, there is no blackening (good), 1 to 2 are slightly good (△), and when it is larger than 2, blackening is recognized and defective (X).

N o.. 1 to 4 6 are耐黒varying process specified in the present invention, the pretreatment, which satisfies the requirements paint, flat section, click Rosuka' isolation portion both corrosion ¹ students good der ivy. In addition, N 0.23 and 4 6 that had undergone blackening resistance also had excellent blackening resistance. On the other hand, Nos. 4 7 to 4 9 deviated from the requirements of the present invention, and the corrosion resistance was poor. 1

(Note) ○: Beautiful hairline is observed.

Δ: Hairline cannot be clearly observed.

X: No hairline exists.

Table 2

〇: Beautiful hairline 〇: The size is attached to the sander.

△: The hairline is clear X: The size is attached to the sander X: White wrinkles are prominent and ^ S cannot be changed les Grinding ability decreases greatly X: Hairline is wrinkled

do not do

Table 3

〇: Beautiful hairline 〇: Force, or sand can be observed on the sander

△: The hairline is clear.

X: Hairline exists

do not do

u Zhen plating composition Wisteria treatment Pretreatment Paint type μ τη

Zn-llAl-3Mg-0. 2Si None Chromome 10

Zn-llAl-3Mg-0. 2Si None Chromed 20

Zn-llAl-3Mg-0. 2Si None Chromome 50

Zn-llAl-3 g-0. 2Si None Chromome 200

Zn-llAl-3Mg-0. 2Si None Chromeme 10 Melamine Ano Liquid 0.5

Zn-llAl-3 g-0. 2Si None Chromate 10 Melamine methanol 2

Zn-llAl-3Mg-0. 2Si None Chromate 10 Melamine methanol 3

Zn-llAl-3Mg-0. 2Si None Chromate 10 Melamine methanol 5

Zn-llAl-3Mg-0. 2Si None Chromate 10 Melamine methanol 25

Zn-llAl-3Mg-0. 2Si None Chromate 10 Melamine alkyd 100

Zn-llAl-3Mg-0. 2Si None Chromeme cake 10 Polyesterol 0.5

Zn-llAl_3Mg-0. 2Si None Chromate 10 Polyesterol 2

Zn-llAl-3Mg-0. 2Si None Chromeme cake 10 Polyesterol 3

Zn-11A 3Mg-0.2Si None Chromate 10 Polyester 5

Zn-llAl-3Mg-0. 2Si None Chromate 10 Polyester 25

Zn-llAl-3Mg-0. 2Si None Chromeme 10 Polyesterol 100

Zn-llAl-3 g-0. 2Si None Chromome 10 Acryl 0.5

Zn-llAl-3 g-0. 2Si None Chromome 10 Acryl 2

Zn-llAl-3Mg-0. 2Si None Chromate 10 Acryl 3

Zn-llAl-3Mg-0. 2Si None Chromate 10 Acryl 5

Zn-llAl-3Mg-0. 2Si None Chromate 10 Acrylic 25

Zn-llAl-3Mg-0. 2Si None Chromate 10 Acryl 100

Zn-llAl-3Mg-0. 2Si Yes Chromate 10 Acrylic 100

Zn-llAl-3Mg-0. 2Si None Chromate-free 10yo

Zn-llAl-3Mg-0. 2Si None Chromate-free 20

Zn-llAl-3 g-0. 2Si None Chromate-free 50

Zn-llAl-3Mg-0. 2Si None Chromate-free 1000

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Melamine alkyd 0.5

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Melamine alkyd 2

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Melamine methanol 3

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Melamine alkyd 5

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Melamine alkyd 25

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Melamine alkyd 100

Zn-llAl-3 g-0. 2Si None Chromate-free 10. Polyester 0.5

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Polyester 2

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Polyesterol 3

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Polyester 5

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Polyester 25

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Polyesterol 100

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Acryl 0.5

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Acryl 2

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Acrylic 3

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Acryl 5

Zn-11A 3Mg- 0. 2Si None Chromate-free 10 Acryl 25

Zn-llAl-3Mg-0. 2Si None Chromate-free 10 Acryl 100

Zn-llAl-3Mg-0. 2Si Yes Chromate-free 10 Acryl 100

Zn-llAl-3 g-0. 2Si None None None

Zn-llAl-3Mg-0. 2Si None Chromate 0.5 None

Zn-llAl-3Mg-0. 2Si None Chromate 10 Acryl 0.4

20

Difference 'replacement paper (纖 (Continued)

○: White wrinkle occurrence 1% or less ○: Blister less than 2mm ○: Less than 1E1 X: White blue occurrence 10% or more X: Blister 2 咖 or more △: E = 1 to 2

X: Greater than 1E2

20/1 Industrial applicability

The highly corrosion-resistant zinc-plated steel material having a hairline appearance according to the present invention has a good hairline appearance and excellent corrosion resistance. Therefore, it is similar to the use of a stainless steel material having a conventional hairline appearance. It can be applied to applications. Moreover, it can be supplied at a lower price than expensive stainless steel materials.

twenty one

Claims

1. Amount of plating is 10 to 60,000 g / m ² , 1 to 60 mass% of A 1 and 0.1 to 10 mass% of 1 ^ ₈ , the balance being Zn and inevitable A hairline formed on the surface of the plating layer made of impurities, the hairline having a surface roughness Ra in the direction perpendicular to the hairline of 0.2 to 2.5 μm and a surface roughness in the direction of the hairline. The

R a is 0.1 to 1.2 μπι, and the surface roughness Ra in the direction perpendicular to the hairline is 1.2 times or more the surface roughness Ra in the hairline direction. Hairline appearance

High corrosion resistance Zn-based alloy steel.

2. coating weight is 1 0 "'~ 6 0 0 g / m 2, the A 1:! ~ 6 0 mass%, 1 ^ _§ a 0.1 to 1 contains 0 wt%, is囲残portion It has a hairline formed on the surface of the plating layer consisting of Zn and inevitable impurities, and the hairline has a number of peaks in the direction perpendicular to the hairline PPI of 50 to 400, and a number of peaks in the direction of the hairline PPI force S 1 〜: 100, and PPI in the direction perpendicular to the hairline is in the direction of the hairline; high corrosion resistance with a hairline appearance characterized by being more than 2.0 times the PPI Z n Alloy steel with steel.

3. With a coating weight of 10 to 600 g Zm ² and A 1:! ~ 60% by mass, _§ 0.1 ~ 10% by mass, the balance has a hairline formed on the surface of the plating layer consisting of Zn and inevitable impurities, the hairline is a hairline The surface roughness Ra in the direction perpendicular to the surface is 0.1 to 2.5 μπι, the number of peaks Ρ Ρ Ι is 50 to 400, and the surface roughness Ra in the hairline direction is 0.1 to 1.2 μ πι, number of peaks Ρ Ρ force 1 ~: L 0 0, and the surface roughness Ra in the direction perpendicular to the hairline is 1.2 times the surface roughness Ra in the hairline direction, A hairliner characterized in that the PPI in the direction perpendicular to the hairline is at least 2.0 times the PPI in the hairline direction.

twenty two High corrosion resistance Zn alloy galvanized steel with a tin appearance.

4. The highly corrosion-resistant Zn system having a hairline appearance according to any one of claims 1 to 3, wherein the plating layer further contains 0.001 to 3% by mass of ≤ 1 Alloy steel.

5. plated layer to be et al., Containing the T i 0.0 0 0 1 to 0.1 mass ^_0/0, B a 0.0 0 0 1 to 0.1 or 1 wt% or two 5. A highly corrosion-resistant zinc-based alloy-plated steel material having a hairline appearance according to any one of claims 1 to 4.

6. The plating layer has a volume fraction of binary eutectic of Zn and A 1 from 1 to 80 V o 1%, and a ternary eutectic of Zn, A 1 and Z nMg alloy has a volume fraction of 10 The highly corrosion-resistant Zn-based alloy-plated steel material having a hairline appearance according to any one of claims 1 to 5, wherein ~ 90 V 0 1%, and the total of both is 50% or more.

7. The highly corrosion-resistant Zn-based alloy having a hairline appearance according to any one of claims 1 to 6, wherein the plating layer has a chromate-treated layer of l to 100 mg / m ^2. Metal steel.

8. The highly corrosion-resistant Zn system having a hairline appearance according to any one of claims 1 to 6, wherein the plating layer has a chromium-free treatment layer containing no chromium in an amount of 1 to 20 O mg Zm ^2. Alloy-plated steel.

9. The highly corrosion-resistant Zn-based alloy having a hairline appearance according to any one of claims 1 to 8, wherein the surface has a transparent resin film layer having a thickness of 0.5 to 100 μm. Metal steel.

1 0. In the vicinity of the interface between the plating layer surface and the chromium-free treatment layer containing no chromium, one or more metal states or hydroxide states of Co, Fe, Ni, Pt, and Mn The deposit layer is 0.1 to 10 mg / m ² and is excellent in resistance to blackening in a wet environment.

twenty three A highly corrosion-resistant zinc-based alloy-plated steel material having a hairline appearance according to any one of claims 1 to 9.

twenty four