JP3511972B2 - Heavy corrosion-resistant coated steel with excellent adhesion durability and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heavy anticorrosion coated steel material having excellent adhesion durability and a method for producing the same, and particularly to maintain stable anticorrosion performance for a long period of time even in a severe corrosive environment such as a marine environment. It is what

[0002]

Steel pipe piles, steel sheet piles and steel pipe sheet piles are mainly used in the marine environment and are exposed to a corrosive environment having a large corrosion rate of about 0.1 to 0.5 mm / y. Therefore, the following anticorrosion methods have been conventionally taken. 1) Anticorrosion coating (tar epoxy resin coating, etc.), 2) Organic lining (polyurethane coating, polyolefin coating), 3) FRP cover + anticorrosion material, 4) Cement mortar lining, and recently, such as Tokyo Bay Crossing Bridge 5) A method in which titanium is wound around a steel pipe pile or the like by welding has been put into practical use (for example, JP-A-7-166568, JP-A-8-254949, JP-A-8-257635, etc.).

However, all of the above-mentioned conventional techniques have the following problems. That is, although the method of using the anticorrosion paint or organic lining of 1) or 2) is relatively inexpensive, it causes the adhesion deterioration of the coating due to a corrosion reaction in a severe environment such as a marine environment, and has a problem that the anticorrosion life is limited. was there.

The 3) FRP cover + anticorrosive material has a disadvantage in that the construction cost is high and the anticorrosion cost per unit area is high. In the cement mortar lining of 4), seawater diffused in the cement and the life of the anticorrosion layer was only about 10 years. The metal-wrapped steel pipe of 5) has problems in that it is difficult to apply it to steel sheet piles and steel pipe sheet piles, in addition to the problem of galvanic corrosion in the portion in contact with the base steel, and that the coating cost is high.

As described above, none of the conventional anticorrosion methods is always satisfactory in terms of anticorrosion effect and construction cost. Normally, there are 10
Since it is designed with a life span of more than a year and is also a public infrastructure, it has been desired to develop an anticorrosion method that is inexpensive and can be expected to have a long life span.

[0006]

DISCLOSURE OF THE INVENTION The present invention advantageously responds to the above-mentioned demands, and is capable of maintaining stable anticorrosion performance for a long period of time even under a severe corrosive environment such as a marine environment. Heavy-duty anticorrosion coated steel with excellent properties
The aim is to propose together with its advantageous manufacturing method.

[0007]

That is, the gist of the present invention is as follows. (1) An organic resin primer layer is provided on the surface of the steel material, and a polyurethane resin layer is provided on the organic resin primer layer.
Furthermore, an acrylic adhesive layer is provided on the polyurethane resin layer, and a thickness of 0.1 mm or less is further provided on the acrylic adhesive layer.
A heavy corrosion-resistant coated steel material having excellent adhesion durability, which is characterized by having a Ti layer. (2) Adhesion according to (1), wherein the acrylic pressure-sensitive adhesive layer has a polyolefin resin as a base material and has an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier on both upper and lower surfaces of the base material. Heavy-duty anticorrosion coated steel material with excellent durability. (3) In (1), the heavy duty anticorrosion coated steel material having excellent adhesion durability, wherein the acrylic pressure-sensitive adhesive layer is made of an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier. (4) In any one of (1) to 3, the organic resin primer layer is a polyurethane resin primer layer, which is a heavy corrosion-resistant coated steel material having excellent adhesion durability. (5) An organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of the cleaned steel material, and then an acrylic adhesive material is laminated on the polyurethane resin layer, and then the acrylic adhesive material. Thickness 0.1 mm on top
A method for producing a heavy corrosion-resistant coated steel material having excellent adhesion durability, which comprises laminating the following Ti foils and crimping them with a crimping roll. (6) A Ti foil having a thickness of 0.1 mm or less in which an organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of a cleaned steel material and then an acrylic adhesive material is laminated on the polyurethane resin layer. A method for producing a heavy corrosion-resistant coated steel material having excellent adhesion durability, characterized in that the Ti foil is pressure-bonded with a pressure-bonding roll with the surface on which the acrylic pressure-sensitive adhesive material is laminated as a lamination surface. (7) In (5) or (6), the acrylic pressure-sensitive adhesive material has a polyolefin resin as a base material and has an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier on both upper and lower surfaces of the base material. A method for producing a heavy corrosion resistant coated steel material having excellent adhesion durability. (8) An organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of the cleaned steel material, and then an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier is applied onto the polyurethane resin layer. After coating by any one of spray coating, roll coater coating, and brush coating to form an acrylic pressure-sensitive adhesive layer , Ti foil with a thickness of 0.1 mm or less is then pressure-bonded on the acrylic pressure-sensitive adhesive layer. A method for producing a heavy corrosion-resistant coated steel material having excellent adhesion durability, which is characterized by crimping. (9) An organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of the cleaned steel material, and then an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier is applied onto the polyurethane resin layer. A feature that a Ti foil with a thickness of 0.1 mm or less applied by spray coating, roll coater coating, or brush coating is pressure-bonded with a pressure-bonding roll with the acrylic pressure-sensitive adhesive-coated surface as a laminated surface. A method for producing a heavy corrosion resistant coated steel material having excellent adhesion durability.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The basic constitution of the present invention can be classified into an organic resin primer (adhesive) layer 1, an organic intermediate layer 2, an intermediate adhesive layer 3 and a Ti layer 4, as shown in FIG. 1, and such coating layers were sequentially cleaned. The surface of the steel material 5 is coated.

As the cleaning treatment for the steel surface, first, it is preferable to completely remove the oxide scale on the steel sheet surface. This is because the oxide scale not only has poor adhesion to the organic resin but is also brittle. As the cleaning treatment, a blasting treatment that can effectively remove dirt and oxide scale on the surface and can impart unevenness to the surface to obtain higher adhesion to the organic resin primer layer is suitable.

The surface of the steel material may be subjected not only to cleaning treatment but also to surface treatment such as chromate treatment or coupling treatment. The organic resin primer layer is adhered to the surface of the steel material and is formed to shield the surface of the steel material from the outside and to obtain corrosion resistance. As such an organic resin primer layer, a urethane-based organic resin primer layer (for example, a polyurethane primer) having good adhesion to the surface of the steel material and good adhesion to the polyurethane resin layer of the organic intermediate layer
Are particularly advantageously matched.

The thickness of this organic resin primer layer is usually 10 μm for cleaning the steel surface by blasting.
If it is less than 100 μm, the adhesive effect is weak, while if it exceeds 100 μm, it becomes expensive and the residual stress of the coating layer increases, so
The thickness is preferably about 100 μm. The organic intermediate layer is Ti
It is provided to avoid electrical contact between the layer and the surface of the steel material. In the present invention, a polyurethane resin layer using a polyurethane resin is used. Polyurethane resin is not only stable in seawater, but also has excellent adhesiveness because it has a urethane bond.

If the thickness of this organic intermediate layer (polyurethane resin layer) is less than 1 mm, the resistance to impact is not sufficient when driftwood or the like hits the anticorrosion layer, so the thickness is set to 1 mm or more, preferably 2 mm or more. Is desirable. However, 5 mm
If it exceeds, the cost increases, so the upper limit is preferably about 5 mm. Further, since the Ti layer has poor adhesiveness, an intermediate adhesive layer that connects the polyurethane resin layer and the Ti layer is provided in the present invention. In the present invention, the intermediate adhesive layer is a layer made of an acrylic adhesive material. The acrylic pressure-sensitive adhesive layer is formed by applying an acrylic pressure-sensitive adhesive, or is a double-sided pressure-sensitive adhesive sheet or the like in which a polyolefin resin is used as a base material and acrylic adhesive is applied to both the upper and lower surfaces of the base material. It is preferable to form the adhesive material by laminating it. Polyolefin resin has a small water absorption rate and excellent water resistance, and is suitable for anticorrosion applications such as marine environments.

The acrylic pressure-sensitive adhesive contains an acrylic resin and a tackifier, and examples of the tackifier include modified rosin, rosin derivative and polyterpene resin. The acrylic pressure-sensitive adhesive is a semi-solid or liquid adhesive obtained by appropriately mixing these tackifiers with an acrylic resin. The thickness of the intermediate adhesive layer (acrylic pressure-sensitive adhesive layer) is preferably about 0.010 to 5 mm. Thickness of acrylic adhesive layer is 0.010 mm
If it is less than 5 mm, the adhesive effect due to adhesion is small, and it becomes difficult to handle it as an intermediate adhesive layer. On the other hand, if it exceeds 5 mm, a creep phenomenon occurs and it is economically disadvantageous. From the viewpoint of adhesive strength, the thickness is more preferably 0.040 mm or more.

The Ti layer is preferably in accordance with JIS first type. Because this material has a large elongation and a large deformability, it can be easily adhered and attached to various shapes. The role of the Ti layer in the present invention is to block corrosion-causing substances such as water, oxygen, and ions that permeate the organic resin layer. Therefore, the thickness of the Ti layer may be quite small. Currently 0.01
Since the manufacturing limit is about mm, it is preferable to set this as the lower limit.
Properly, the upper limit shall be the in 0.1 mm or. This is because as the thickness increases, the cost of Ti material increases and the deformability at the time of pressure bonding becomes a problem.

The surface treatment of the Ti layer is not particularly limited, but it may be subjected to pickling treatment, chromate treatment, coupling agent coating, or surface treatment in which these are combined. Next, a method of manufacturing the above-described heavy anticorrosion coated steel material will be described. First, an organic resin primer layer is formed by spray coating on the surface of the surface-purified steel material. The organic resin primer is preferably spray-coated so that the thickness of the organic resin primer layer is in the range of 0.010 to 0.100 mm (10 to 100 μm). A polyurethane primer is particularly advantageously applied as the organic resin primer. In addition,
As a cleaning treatment of the steel material surface, it is preferable to perform a blast treatment capable of completely removing the oxide scale on the surface.

Then, a polyurethane resin layer as an organic intermediate layer is formed on the organic resin primer layer by spray coating. The thickness of the polyurethane resin layer is 1
It is preferable to spray-coat the polyurethane resin so as to be in the range of 5 mm. Further, in the production of the heavy anticorrosion coated steel material of the present invention, the polyurethane primer advantageously applied for forming the organic resin primer layer and the polyurethane resin used for forming the organic intermediate layer are usually 2 A liquid reaction type resin is used, but since the cross-linking reaction rate is generally high, spray coating is most suitable.

Next, a Ti layer is formed on the polyurethane resin layer with an intermediate adhesive layer (acrylic adhesive layer) interposed therebetween. In order to bond the Ti layer to the polyurethane resin layer via the intermediate adhesive layer (acrylic pressure-sensitive adhesive layer), it is essential to apply pressure, but before these polyurethane resin layers are sufficiently cured (curing rate: When a Ti layer is laminated on (50% or less),
The polyurethane resin layer is deformed, and the film thickness is reduced. Therefore, after confirming the curing by touching with a finger, it is preferable to perform Ti pressure bonding with a curing degree of 50% or more for complete curing.

Further, in order to form a Ti layer on the polyurethane resin layer, an acrylic adhesive material which serves as an intermediate adhesive layer is laminated on the polyurethane resin layer, and then a Ti foil is laminated on the acrylic adhesive material by a pressure roll. It is preferable to crimp. As the acrylic pressure-sensitive adhesive material, it is preferable to use a polyolefin resin as a base material, and apply an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier to both upper and lower surfaces of the base material. Also,
You may laminate | stack an acrylic adhesive material on Ti foil, laminate | stack on the polyurethane resin layer by making the surface which laminated | stacked the acrylic adhesive material into a lamination surface, and pressure-bond it with a pressure bonding roll.

In order to form a Ti layer on the polyurethane resin layer, an acrylic pressure-sensitive adhesive to serve as an intermediate adhesive layer may be applied on the polyurethane resin layer, and then a Ti foil may be pressure-bonded by a pressure-bonding roll. The acrylic pressure-sensitive adhesive is preferably applied by any one of spray coating, roll coater coating and brush coating. Spray coating is most suitable for deformed materials such as steel sheet pile and steel pipe sheet pile. The acrylic adhesive may be applied on the Ti foil instead of on the polyurethane resin layer without any problem. In this case, Ti
The surface of the foil coated with the acrylic pressure-sensitive adhesive is used as a laminated surface and pressure-bonded onto the polyurethane resin layer. When the acrylic pressure-sensitive adhesive is applied on the Ti foil, it is preferable to use a roll coater whose film thickness can be easily controlled.

On the polyurethane resin layer or Ti
The thickness of the acrylic adhesive layer laminated on the foil is 0.010 to 5 mm
It is preferable to adjust the thickness of the acrylic pressure-sensitive adhesive material to be within the range. Also, on the polyurethane resin layer or Ti
The thickness of the acrylic pressure-sensitive adhesive applied on the foil is preferably such that the thickness of the acrylic pressure-sensitive adhesive layer is in the range of 0.010 to 5 mm.

To press the Ti foil onto the polyurethane resin layer via the intermediate adhesive layer (acrylic adhesive layer),
It is preferable to use a pressure bonding roll. Using a crimp roll
The pressure bonding of the Ti foil is effective in terms of continuous production and also in terms of preventing entrapment of bubbles at the interface between the intermediate adhesive layer (acrylic pressure-sensitive adhesive layer) and the Ti layer or the polyurethane resin layer. The pressing force of the crimp roll is 0.098 to 294 N / cm.
(0.01 to 30 kgf / cm) is suitable. Further, it is more preferably 9.8 to 29.4 N / cm (1.0 to 3.0 kgf / cm 2).

The roll material may be plastic or metal.

[0023]

EXAMPLES The steel materials used in the examples were manufactured as follows. After descaling the surface of the steel sheet pile by blasting, a urethane-based primer (organic resin primer) was applied by airless spraying to a predetermined thickness to form an organic resin primer layer. Then, after confirming that the resin was cured by touching with a finger, a polyurethane resin was applied to a predetermined thickness by airless spraying to form a polyurethane resin layer. Then, after confirming that the polyurethane resin layer has been cured by touching with fingers, an acrylic adhesive sheet as an intermediate adhesive layer and a titanium sheet (Ti foil) having a predetermined thickness as a Ti layer are sequentially laminated, and a silicone sheet is formed. Using a rubber roll, pressing force: 15N / cm, titanium sheet (Ti
It was attached so as to be pressed in the direction of the steel material (steel sheet pile) from the foil side, and pressure-bonded to the polyurethane resin layer via the intermediate adhesive layer. (This Ti layer forming method is hereinafter referred to as A method) Further, for some steel materials (steel sheet pile), an acrylic adhesive sheet as an intermediate adhesive layer is laminated on a Ti foil, and the acrylic adhesive sheet is used. Using the laminated surface as a laminated surface, pressure was applied to the polyurethane resin layer with a pressing force of 15 N / cm using a silicone rubber roll. (The method of forming this Ti layer is described below.
Note that, as the acrylic adhesive material, Nitto Denko adhesive sheets (No.5710, No.5711, No.5713) having different thicknesses were used.

Regarding some steel materials (steel sheet pile),
As an intermediate adhesive layer on the polyurethane resin layer, an acrylic pressure-sensitive adhesive (acrylic resin, containing a modified rosin and a rosin derivative as a tackifier) is applied with a brush, and then a Ti foil is laminated on the intermediate adhesive layer. A silicone rubber roll was used for pressure bonding with a pressing force of 15 N / cm. (The method for forming this Ti layer is hereinafter referred to as C method) The steel sheet pile having the coating layer having a predetermined film thickness formed on the surface in this manner was subjected to the anticorrosion performance test and the impact resistance test.

In the anticorrosion performance test, the test piece is immersed in a 3% NaCl solution (80 ° C.) in order to simulate and promote the anticorrosion property in a marine environment (immersion time 60 days).
And evaluated by the peeling distance from the end face. Regarding impact resistance, a weight of 3 kg was dropped from a height of 1 m, and the damage state of the coating was investigated. The results of this examination were evaluated as follows: ◯: No damage / defects, Δ: Defects in the coating, ×: Damage to the steel surface was observed.

Table 1 shows the examination results when the coating layer was formed by the method A, Table 2 shows the examination results by the method B, and Table 3 shows the method C. In case of
Shown respectively.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

With respect to Test Nos. 9 (Comparative Example) and No. 10 (Inventive Example), anticorrosion performance tests were conducted by further immersing them in a 3% NaCl solution (60 ° C.) for a long period (up to 120 days). The change in the peel distance from the end face was investigated. The result is shown in FIG. According to the present invention, when the surface of the steel material is sequentially coated with an organic resin primer layer, a polyurethane resin layer, an acrylic pressure-sensitive adhesive layer and a Ti layer, regardless of the method of forming the coating layer, excellent corrosion resistance and Impact resistance is obtained.
Further, as shown in FIG. 2, it can be seen that the example of the present invention can exhibit the anticorrosion property for a long period of time as compared with the conventional organic resin-coated one (comparative example).

[0031]

As described above, according to the present invention, it is possible to provide a coated steel material having a stable anticorrosion performance for a long period of time, whereby a structure for a long period of time can be constructed in a severe corrosive environment such as a marine environment. This makes it possible to supply an inexpensive structure, resulting in a remarkable industrial effect.

[Brief description of drawings]

FIG. 1 is a diagram showing a basic coating structure of the present invention.

FIG. 2 is a graph showing the influence of the immersion period on the separation distance from the end face in the inventive example and the comparative example.

[Explanation of symbols]

1 Organic resin primer layer 2 Polyurethane intermediate layer 3 Intermediate adhesive layer 4 Ti layer 5 Steel

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-7-100527 (JP, A) JP-A-8-71763 (JP, A) JP-A-11-207481 (JP, A) JP-A-7- 26227 (JP, A) JP 63-183838 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 B05D 1/00-7/24 C23C 28/00

Claims (9)

(57) [Claims] 1. A steel material having an organic resin primer layer on the surface thereof, a polyurethane resin layer on the organic resin primer layer, and an acrylic adhesive layer on the polyurethane resin layer. No thickness on the acrylic adhesive layer .
A heavy anticorrosion coated steel material having excellent adhesion durability characterized by having a Ti layer of 1 mm or less . 2. The acrylic pressure-sensitive adhesive layer according to claim 1, wherein the polyolefin resin is a base material, and acrylic adhesives containing an acrylic resin and a tackifier are provided on both upper and lower surfaces of the base material. Heavy anticorrosion coated steel material with excellent adhesion durability. 3. The heavy anticorrosion coated steel material having excellent adhesion durability according to claim 1, wherein the acrylic pressure-sensitive adhesive layer is made of an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier. 4. The method according to any one of claims 1 to 3,
A heavy corrosion resistant coated steel material having excellent adhesion durability, wherein the organic resin primer layer is a polyurethane resin primer layer. 5. An organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of a cleaned steel material, and then an acrylic adhesive material is laminated on the polyurethane resin layer, and then the acrylic resin material is laminated. Thick on adhesive
A method for producing a heavy corrosion-resistant coated steel material having excellent adhesion durability, which comprises laminating Ti foils having a thickness of 0.1 mm or less and crimping them with a crimping roll. 6. An organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of a cleaned steel material, and then an acrylic adhesive material is laminated on the polyurethane resin layer to a thickness of 0.1 mm or less. A method for producing a heavy-corrosion-coated steel material having excellent adhesion durability, characterized in that a Ti foil is pressure-bonded with a pressure-bonding roll, with a surface of the Ti foil on which an acrylic adhesive material is laminated being a lamination surface. 7. The acrylic pressure-sensitive adhesive material according to claim 5, wherein the acrylic pressure-sensitive adhesive has a polyolefin resin as a base material, and has an acrylic pressure-sensitive adhesive containing an acrylic resin and a tackifier on both upper and lower surfaces of the base material. A method for producing a heavy corrosion resistant coated steel material having excellent adhesion durability. 8. An organic resin primer layer and a polyurethane resin layer are sequentially formed by spray coating on the surface of a cleaned steel material, and then an acrylic adhesive containing an acrylic resin and a tackifier is applied on the polyurethane resin layer. The agent is applied by spray coating, roll coater coating, or brush coating to form an acrylic pressure-sensitive adhesive layer, and then a thickness of 0.1 mm or less is applied on the acrylic pressure-sensitive adhesive layer .
A method for producing a heavy corrosion-resistant coated steel material having excellent adhesion durability, which is characterized by crimping a Ti foil with a crimping roll. 9. An acrylic adhesive containing an acrylic resin and a tackifier on the surface of a cleaned steel material by sequentially spraying an organic resin primer layer and a polyurethane resin layer onto the polyurethane resin layer. A Ti foil with a thickness of 0.1 mm or less applied by spray coating, roll coater coating, or brush coating with the agent is pressure-bonded with a pressure-bonding roll with the surface coated with the acrylic adhesive as the laminated surface. A method for producing a heavy corrosion-resistant coated steel material having excellent adhesive durability.