JPH06115003A - Decorative polyolefin coated steel - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a designable polyolefin-coated steel material in which the surface of the polyolefin coating has various patterns, is in harmony with the environment, and prevents peeling of the coating and fading due to ultraviolet rays. [Structure] A surface of the steel material 1 which is required to have an aesthetic appearance is subjected to a surface treatment, and a black polyolefin layer 5 to which carbon black is added through a modified polyolefin adhesive layer 4, a vinyl acetate adhesive layer 6, an antioxidant and ultraviolet rays. Polyolefin chloride layer or polyethylene terephthalate layer 7 containing an absorber, printed pattern layer 8, transparent acrylic resin film 9 containing an ultraviolet absorber and transparent fluororesin film 9 are laminated in this order to provide a design polyolefin coating Steel material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to steel structure members such as steel sheet piles, H-section steels, section steels for connecting walls, steel pipe piles, square steel pipe piles, steel pipe sheet piles and steel plates used in the ocean, rivers and harbors. Regarding the polyolefin-coated steel used, more specifically, it has a printed pattern of granite, stone wall, etc. on the surface, which is in harmony with the environment, has excellent weather resistance by preventing fading of the printed pattern due to ultraviolet rays, and has a polyolefin-coated and printed pattern. The present invention relates to a designable polyolefin-coated steel material having excellent adhesiveness.

[0002]

2. Description of the Related Art Conventional heavy anticorrosion coated steel materials, especially polyolefin coated steel materials, are coated with polyolefin such as black polyethylene having excellent corrosion resistance.

However, due to the recent increasing market needs for the aesthetic appearance of steel structures in cityscapes, rivers and harbors, the development of polyolefin coated steel materials that have various patterns, are in harmony with the environment and are excellent in corrosion resistance. Is desired.

To meet such needs, a method of adhering a pattern-printed plastic sheet such as polyvinyl chloride or polyethylene terephthalate having a pattern printed on its surface with some kind of adhesive may be considered.

[0005]

However, since the heavy-corrosion-coated steel material is used for a long period of time, for example, a pattern-printed polyvinyl chloride sheet is used as a conventional black polyethylene-coated steel sheet pile with commercial ethylene-vinyl acetate as an adhesive. When adhered to the surface and subjected to an actual exposure test in a river, the pattern-printed polyvinyl chloride sheet is discolored by the ultraviolet rays in the sun rays to impair its aesthetic appearance, and the pattern-printed polyvinyl chloride sheet peels from the surface of the black polyethylene coating. There was a problem.

As described above, it has been difficult with the prior art to prevent fading of the pattern of the pattern-printed plastic sheet and to simultaneously obtain the adhesiveness between the pattern-printed plastic sheet and the black polyolefin coating.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a black polyolefin containing carbon black is added to the surface of a steel material that has been subjected to a surface treatment through a modified polyolefin adhesive. Vinyl acetate adhesive layer consisting of specific component ethylene-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer or acrylic monomer-ethylene-vinyl acetate copolymer on the surface of the adhered steel , A polyvinyl chloride sheet containing an antioxidant and an ultraviolet absorber or a printing support film made of polyethylene terephthalate, a printed pattern layer and a transparent acrylic resin film containing an ultraviolet absorber, and a transparent fluororesin film are laminated by sequentially laminating the above. The inventors have found that the above problem can be solved and have reached the present invention.

That is, according to the present invention, for example, as shown in FIGS. 1 to 8, the surface of a steel material 1 such as a steel plate, a steel sheet pile, an H-section steel, a wall section steel, a steel pipe pile, a square steel pipe pile, and a steel pipe sheet pile is blasted. The scale is removed by a treatment or the like, the chromate film 2 and the epoxy primer layer 3 are sequentially laminated and subjected to a base treatment, and 0.1 to 5% by weight of carbon black is contained on the surface thereof through the modified polyolefin adhesive layer 4. Black polyolefin layer 5, ethylene-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer or acrylic monomer-
Contains a vinyl acetate adhesive layer 6 made of ethylene-vinyl acetate copolymer, a print support film 7 made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer 8 and an ultraviolet absorber Transparent acrylic resin film 9, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride,
A designable polyolefin coating characterized in that a transparent fluororesin film 10 comprising a tetrafluoroethylene-hexafluoropropylene copolymer, an ethylene-tetrafluoroethylene copolymer or a vinylidene fluoride-hexafluoropropylene copolymer is sequentially laminated. It is a steel material.

The present invention will be described in detail below.

The steel materials used in the present invention are steel plates made of alloy steel such as carbon steel and stainless steel, steel sheet piles, H-section steels, section steels for wall walls, steel pipe piles, square steel pipe piles and steel pipe sheet piles.

Further, for the purpose of improving the corrosion resistance of the steel material, the surface is plated with zinc, aluminum, chromium or the like, zinc-
It is also possible to use an alloy plating of aluminum, zinc-nickel or the like, or a plating obtained by subjecting the plating or alloy plating to dispersion plating in which inorganic fine particles such as silica or titanium oxide are dispersed.

As the polyolefin used for forming the modified polyolefin adhesive layer 4 and the black polyolefin 5 of the present invention, polyethylene, polypropylene, or propylene, 1-butene, 4-methyl-1-pentene, 1-
A copolymer of α-olefin such as hexene and 1-octene and ethylene is used.

As the modified polyolefin adhesive, a modified polyolefin obtained by modifying a polyolefin with an acid anhydride such as maleic anhydride, a modified polyolefin prepared by adding an elastomer such as ethylene-propylene rubber to the polyolefin with an acid anhydride, or Adhesives obtained by diluting these modified polyolefins with polyolefins are used, but polyolefin-based adhesives other than these can also be used.

To prevent the fading of the printed pattern due to ultraviolet rays, 0.1 to 5% by weight of carbon black is added to the black polyolefin layer 5.

If the amount of the carbon black added is less than 0.1% by weight, fading of the printed pattern cannot be prevented, and if it exceeds 5% by weight, the water-resistant adhesion to the printing plastic sheet deteriorates, which is not desirable.

The vinyl acetate adhesive 6 may be a binary copolymer of ethylene and vinyl acetate or ethylene, a terpolymer of vinyl acetate and vinyl chloride or an acrylic monomer.

Here, acrylic acid, methacrylic acid, acrylonitrile, or an ester of acrylic acid or methacrylic acid with methyl alcohol, ethyl alcohol, or propyl alcohol is used as the acrylic monomer.

When a binary copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate copolymer is used, the ethylene content is 50 to 98% by weight and the vinyl acetate content is 2 to 50% by weight. Use the one in the range.

In this case, if the ethylene content is less than 50% by weight and more than 98% by weight, or the vinyl acetate content is less than 2% by weight and more than 50% by weight, a river exposure test is conducted between the black polyolefin coating and the printing support film. Peel off.

When a terpolymer of ethylene, vinyl acetate and vinyl chloride or an acrylic monomer is used, the ethylene content is 45 to 70% by weight and the vinyl acetate content is 2.
The content of the vinyl chloride or the acrylic monomer is 5 to 28% by weight.

In this case, the ethylene content is less than 45% by weight and more than 70% by weight, and the vinyl acetate content is 2% by weight.
When the content is less than 50% by weight and the content of vinyl chloride or acrylic monomer is less than 5% by weight and more than 28% by weight, peeling occurs between the black polyolefin coating 5 and the printing support film 7 in a river exposure test.

As the printing support film 7, polyvinyl chloride or polyethylene terephthalate is used.

A hindered phenol-based antioxidant and a benzotriazole-based UV absorber are added to these printing support films 7 for fading the printed pattern layer.

As hindered phenolic antioxidants, octadecyl-3- (3,5-di-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (t-butyl-5-methyl- 4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4]
-Hydroxyphenyl) propionate] and the like are used.

As octadecyl-3- (3,5-di-butyl-4-hydroxyphenyl) propionate, IRGANOX 1076 manufactured by Japan Ciba-Geigy Co., Ltd. is triethylene glycol-bis [3- (t-butyl-5-methyl-4). -Hydroxyphenyl) propionate] is IRGANOX245 manufactured by Ciba-Geigy Japan,
Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] is IRGANOX1 manufactured by Ciba-Geigy Japan.
010 can be used respectively.

As the ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-- Hydroxyphenyl] propionate-polyethylene glycol condensate or the like is used.

As 2- (5-methyl-2-hydroxyphenyl) benzotriazole, TINUVIN-P manufactured by Ciba-Geigy Co., Ltd. of Japan is methyl-3- [3-t-butyl-5- (2H-benzotriazole-2- Ill) -4
-Hydroxyphenyl] propionate-polyethylene glycol condensate is available from TI
NUVIN 213 can be used respectively.

In order to prevent fading of the printed pattern layer 8 due to ultraviolet rays, the printing support film 7 contains 0.1 to 3% by weight of a hindered phenolic antioxidant and 0% of a benzooriazole ultraviolet absorber. 0.1 to 3 wt% is added.

When the amount of the hindered phenolic antioxidant added to the printing support film 7 is less than 0.1% by weight and the amount of the benzotriazole ultraviolet absorber added is less than 0.1% by weight, the discoloration of the printed pattern layer 8 occurs. When the addition amount of the hindered phenol-based antioxidant exceeds 3% by weight and the addition amount of the benzotriazole-based ultraviolet absorber exceeds 3% by weight, peeling occurs between the print support film 7 and the transparent acrylic resin film 9. To do.

As the transparent acrylic resin film 9, a polymethyl methacrylate, a methyl methacrylate-vinylidene fluoride copolymer or a terpolymer of methyl methacrylate-ethylene-vinylidene fluoride is used. UV absorbers are added in the range of 0.2 to 5% by weight.

The ultraviolet absorber added is 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol condensate and the like are used.

As 2- (5-methyl-2-hydroxyphenyl) benzotriazole, TINUVIN-P manufactured by Ciba-Geigy Co., Ltd. is available as methyl-3- [3-t-butyl-5- (2H-benzotriazole-2-]. Ill) -4
-Hydroxyphenyl] propionate-polyethylene glycol condensate is available from TI
NUVIN 213 can be used respectively.

When the amount of the ultraviolet absorber added to the acrylic resin is less than 0.2% by weight, fading due to ultraviolet rays cannot be prevented,
If it exceeds 5% by weight, it is separated from the transparent fluororesin film 10.

Examples of the transparent fluororesin film 10 include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer or vinylidene fluoride-hexafluoro. A propylene copolymer is used.

When manufacturing the designable polyolefin-coated steel material of the present invention, first, the printing support film 7 obtained by T-die extrusion molding is applied to the impression cylinder 1 with a gravure printing machine as shown in FIG.
1 and ink between the plate cylinder 12 engraved with the pattern of the photograph
At 3, the print pattern layer 8 is printed on the surface of the print support film 7 to form the print pattern sheet 14.

Next, as shown in FIG. 10, a transparent fluororesin and a transparent acrylic resin are supplied from the extruders 15 and 16 to the two-layer T die 17 and extruded to form the transparent fluororesin film 10 and the transparent acrylic resin film 9, respectively. Extruded in the state of a two-layer laminated molten sheet, the transparent acrylic resin film 9 of the two-layer sheet and the printed pattern layer 8 of the printed pattern sheet 14 described above.
Are laminated together to obtain a four-layer laminated sheet 18.

When a black polyolefin resin sheet can be used here, first, a black polyolefin resin is extruded from a single-layer T-die to produce a black polyolefin sheet, which is crosslinked by irradiating it with an electron beam from the surface and then crosslinked with an electron beam. The sheet 5 is manufactured.

Then, as shown in FIG. 11, a single-layer T-die 1
A vinyl acetate adhesive 6 is extruded from 9 in the form of a molten sheet to laminate the 4-layer laminated film 18 and the black polyolefin sheet 5 to produce a 6-layer laminated sheet 20.

Then, the surface of the steel material is grit blasted,
After blasting with sandblasting etc. to remove rust,
A chromate treatment and an epoxy primer are applied and cured to carry out a base treatment, and then a powder of a modified polyolefin adhesive is electrostatically coated to form a modified polyolefin adhesive layer 4, and then the above-mentioned 6-layer laminated sheet 20 is coated. Then, the designable polyolefin-coated steel material of the present invention is obtained.

When a black polyolefin sheet cannot be used, the vinyl acetate adhesive 6 is extruded from the single layer T die into a sheet and laminated on the back surface of the four layer laminated sheet 18 to form a five layer laminated film 32 (see FIG. 1). ) Is manufactured.

Then, the surface of the steel material is grit blasted,
After blasting with sandblasting etc. to remove rust,
A chromate treatment and an epoxy primer are applied and cured to apply a base treatment.

Next, the modified polyolefin adhesive powder is sprayed to form the modified polyolefin adhesive 4, and the surface of the modified polyolefin adhesive powder is sprayed with the black polyolefin resin powder to cover the black polyolefin layer 5.

Then, the above-mentioned five-layer laminated film 32 is pressure-bonded to the surface thereof to obtain the designable polyolefin-coated steel material of the present invention.

According to the gist of the present invention, the modified polyolefin adhesive layer 4, the black polyolefin layer 5, the vinyl acetate adhesive layer 6, the printing support film 7, are formed on the surface of the coated steel material 1.
It suffices that the printed pattern layer 8, the transparent acrylic resin film 9 and the transparent fluororesin film 10 are firmly laminated and coated, and conventionally known chromate treatment, epoxy primer, phosphate treatment, silane coupling treatment alone are used for the base treatment. Alternatively, a combination of these base treatments can be used.

Next, a method for manufacturing the designable polyolefin-coated steel material of the present invention will be described by taking a steel sheet pile as an example.

First, the crests or troughs of the steel sheet pile are blast-treated by grit blasting to remove rust, and then chromate treatment and epoxy primer are applied and cured to carry out a base treatment, and then a modified polyolefin adhesive is applied. The powder is electrostatically coated and melted to form the modified polyolefin adhesive layer 4.

In the coating of the crest surface, the steel sheet pile whose crest surface is coated with the modified polyolefin adhesive layer in a molten state is moved by the conveying roll 21 and the conveying table 22 as shown in FIG. The six-layer laminated sheet 20 of No. 1 is pressure-bonded by a web pressure roller 23, and then the auxiliary roller 2
4. Further, after sequentially crimping with the crimping rolls 25 and 26 of the flange portion, water cooling is performed to obtain the colored polyolefin-coated steel sheet pile (FIG. 2) of the present invention.

In the coating of the valley surface, the steel sheet pile coated with the modified polyolefin adhesive layer in a molten state is moved on the transport roll 21 and the transport table 22 as shown in FIG. The 6-layer laminated sheet 20 of No. 2 is pressure-bonded with the pressure-bonding roll 27 of the web portion, and then the auxiliary roll 2
8, pressure bonding rolls 29 and 30 for the flange portion, and pressure bonding roll 31 for the claw portion are sequentially pressure-bonded, followed by water cooling to obtain the colored polyolefin-coated steel sheet pile (FIG. 3) of the present invention.

As the method of applying the chromate treating agent, conventionally known methods such as roll application, brush application, and ironing application with various brushes can be used.

As a method of applying the epoxy primer, a conventionally known method such as spray coating, ironing with a rubber ring or a rubber spatula can be used.

A method of previously laminating the modified polyolefin adhesive with the six-layer laminated sheet 20 and coating the laminated sheet can also be used.

In the colored polyolefin-coated H-section steel of the present invention shown in FIG. 4, the entire surface of the H-section steel 1 is sandblasted, and the chromate treatment agent 2 is applied and baked.

Next, the epoxy primer 3 is applied to the surface and heated and cured.

On the surface, powder 4 of the modified polyolefin adhesive is sprayed and melted. Then, the five-layer laminated sheet 32 of the present invention is pressure bonded to the surface thereof to obtain the designable polyolefin-coated H-section steel of the present invention.

In the designing polyolefin-coated steel for connecting walls of the present invention shown in FIG. 5, the entire surface of the steel for connecting walls 1 is sandblasted, the chromate treatment agent 2 is applied and baked.

Next, the epoxy primer 3 is applied to the surface and heated and cured.

The modified polyolefin adhesive powder 4 is sprayed on the surface, and then the black polyolefin powder 5 is sprayed.

On the surface of the wall surface, which requires the design of the surface,
The five-layer laminated sheet 32 of the present invention is coated to obtain the shaped polyolefin-coated structural steel for wall connection of the present invention.

In the designable polyolefin-coated steel pipe pile according to the present invention shown in FIG. 6, the outer surface of the steel pipe 1 is grit blasted and the chromate treatment agent 2 is applied and heated and baked while the steel pipe 1 is rotated and run.

Next, the epoxy primer 3 is spray-coated on the surface and heated and cured.

The powder 4 of the modified polyolefin adhesive is electrostatically coated on the surface and melted by the heat of the steel pipe, and then the black polyolefin 5 is extrusion-coated from the T die into a sheet.

Next, the five-layer laminated sheet 32 of the present invention is pressure bonded to obtain the designable polyolefin-coated steel pipe pile according to the present invention.

In the design-use polyolefin coated square steel pipe pile according to the present invention shown in FIG. 7, the outer surface is grit blasted and the chromate treatment agent 2 is applied and heated and baked while the square steel pipe 1 is transferred and transported by the transport table.

Next, the epoxy primer 3 is spray-coated on the surface and heated and cured.

The powder 4 of the modified polyolefin adhesive is electrostatically coated on the surface and melted by the heat of the square steel pipe, and then the black polyolefin 5 is extrusion-coated from a square die into a square tube shape.

Then, the five-layer laminated sheet 32 of the present invention is pressure-bonded to the surface thereof to obtain the designable polyolefin-coated steel pipe pile of the present invention.

In the designable polyolefin-coated steel pipe sheet pile according to the present invention shown in FIG. 8, the outer surface of the steel pipe sheet pile 1 is sandblasted, and the chromate treatment agent 2 is applied and baked.

Next, the epoxy primer 3 is applied to the surface and heated and cured.

On the surface thereof, the modified polyolefin adhesive powder 4 is sprayed, and then the black polyolefin powder 5 is sprayed.

Next, the five-layer laminated sheet 32 of the present invention is pressure-bonded to obtain the designable polyolefin steel pipe sheet pile of the present invention.

As shown in FIGS. 1 to 8, the colored polyolefin-coated steel material of the present invention has a surface of steel material 1 such as steel plate, steel sheet pile, H-section steel, section steel for wall, steel pipe pile, square steel pipe pile, and steel pipe sheet pile. The scale is removed by blasting, etc., the chromate film 2 and the epoxy primer layer 3 are sequentially laminated and subjected to a base treatment, and the modified polyolefin adhesive layer 4 is formed on the surface thereof.
Black polyolefin layer 5 containing 0.1 to 5% by weight of carbon black via ethylene, ethylene-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer or acrylic monomer-ethylene-vinyl acetate copolymer Vinyl acetate adhesive layer 6 made of a polymer, printing support film 7 made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer 8
And a transparent acrylic resin film 9 containing an ultraviolet absorber, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer or vinylidene fluoride- A polyolefin-coated steel material, characterized in that transparent fluororesin films 10 made of a hexafluoropropylene copolymer are sequentially laminated.

The chromate coating 2 has an adhesion of 200 to 1500 mg / m ^{2 in} terms of total chromium adhesion, the epoxy primer coating 3 has a thickness of 10 to 150 μm, the modified polyolefin adhesive layer 4 has a thickness of 100 to 600 μm, The black polyolefin layer 5 has a thickness of 1 to 5 mm, the vinyl acetate adhesive layer 6 has a thickness of 10 to 250 μm, the printing support film 7 has a thickness of 10 to 500 μm, and the printed pattern layer 8 has a thickness of 5 to 50 μm.
The thickness of μm, the transparent acrylic resin film 9 is 10 to 50
Thickness of 0 μm, transparent fluororesin film 10 is 10-5
Good results are obtained with a film thickness of 00 μm.

The present invention will be described below based on examples.

[0074]

【Example】

[0075]

Example 1 First, in a gravure printing machine as shown in FIG.
The printing support film 7 obtained by T-die extrusion molding is inserted between the impression cylinder 11 and the plate cylinder 12 engraved with the pattern of the photo of Ishigaki, and the printing pattern layer 8 is printed on the surface of the printing support film 7 with the ink 13. A printed pattern sheet 14 was created.

Next, as shown in FIG. 10, the transparent fluororesin and the transparent acrylic resin are supplied from the extruders 15 and 16 to the two-layer T die 17 and extruded. The layered molten sheet was extruded and laminated so that the transparent acrylic resin film 9 of the two-layered sheet and the printed pattern layer 8 of the printed pattern sheet 14 were laminated together to obtain a four-layer laminated sheet 18.

On the other hand, a black polyolefin resin was extruded from a single-layer T-die to produce a black polyolefin sheet, which was cross-linked by irradiating it with an electron beam from the surface to produce an electron beam cross-linked black polyolefin sheet 5.

Then, as shown in FIG. 11, a single-layer T-die 1
A vinyl acetate adhesive 6 was extruded from 9 in the form of a molten sheet to laminate the 4-layer laminated film 18 and the black polyolefin sheet 5 to produce a 6-layer laminated sheet 20. The composition of the 6-layer laminated sheet is shown below.

Black polyolefin layer Resin: Electron beam cross-linked polyethylene Carbon black Addition amount: 0.1% by weight Film thickness: 2 mm

Vinyl acetate adhesive layer Resin: ethylene-vinyl acetate copolymer (ethylene content: 50% by weight) Film thickness: 30 μm

Printing support film Resin: polyvinyl chloride Antioxidant: IRGANOX1 manufactured by Ciba-Geigy Japan
076 Antioxidant addition amount: 0.1% by weight UV absorber: TINUVIN manufactured by Ciba-Geigy Japan
-P UV absorber addition amount: 0.1% by weight Film thickness: 200 μm

Pattern printing layer Ink: Fluorine-based ink Thickness: 10 μm

Transparent acrylic resin film Resin: Polymethylmethacrylate UV absorber: TINUVIN manufactured by Ciba-Geigy Japan
-P UV absorber addition amount: 0.1% by weight Thickness: 50 μm

Transparent fluororesin film Resin: Polyvinylidene fluoride Thickness: 50 μm

Next, the crest surface of the steel sheet pile (FSPIII type) is subjected to grit blast treatment to remove rust, and a chromate treatment agent is applied to the crest surface so that the total chromium deposition amount becomes 600 mg / m ² and 160 ° C. It was heated and baked.

While the chromate-treated steel sheet pile was being conveyed by a table roller, an epoxy primer was spray-coated on the surface so that the film thickness was 50 μm, and was heated to 190 ° C. by high frequency induction heating to cure it.

Then, a powder of maleic anhydride-modified polyethylene adhesive was electrostatically coated on the surface so that the film thickness was 250 μ, and the surface was coated with the above-mentioned 6-layer laminated sheet of the present invention. Designed polyethylene coated steel sheet pile N
o. 1 was produced.

In addition, as a comparative example, the conventional design polyethylene-coated steel sheet pile No. 6 coated with the 4-layer laminated sheet lacking the transparent acrylic resin film and the transparent fluororesin film of the above-mentioned 6-layer laminated sheet was used. 32, a designable polyethylene-coated steel sheet pile No. No. 32 coated with a 5-layer laminated sheet lacking a transparent acrylic resin film. 33, a designable polyethylene-coated steel sheet pile No. 3 coated with a 5-layer laminated sheet lacking a transparent fluororesin film. 34 was produced.

These coated steel sheet piles were cut to a length of 1 m,
Exposed to river for 3 years.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results shown in Table 1, the design polyethylene-coated steel sheet pile laminated on the surface of the transparent acrylic resin film and the transparent fluororesin film of the present invention is compared with the conventional design polyethylene-coated steel sheet pile lacking these films. Excellent, with no fading of the pattern or peeling of the coating.

[0092]

Example 2 The designable polyethylene-coated steel sheet pile No. 3 of the present invention in which the amount of carbon black added in the black polyethylene layer in the 6-layer laminated sheet of Example 1 was changed to 2.5% by weight. Two
And the designable polyethylene-coated steel sheet pile No. of the present invention in which the amount of carbon black added was changed to 5% by weight. 3 and as a comparative example, a designable polyethylene-coated steel sheet pile No. 3 to which the carbon black was not added. 35 and a designable polyethylene-coated steel sheet pile N in which the amount of carbon black added is 6% by weight
o. 36 was produced.

These steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

After the exposure, Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating.

From the results of Table 1, together with the results of the exposure test of the designable polyethylene-coated steel sheet pile of the present invention described in Table 1 of Example 1, the amount of carbon black added in the black polyethylene layer of the present invention was Only when the amount is in the range of 0.1 to 5% by weight, there is no discoloration of the printed pattern and peeling of the coating, which is excellent.

However, when the amount of carbon black added is 0.
If it is less than 1% by weight, the anti-fading effect is not obtained, and if it exceeds 5% by weight, the coating is peeled off.

[0097]

Example 3 A book in which the ethylene content of the ethylene-vinyl acetate copolymer used in the vinyl acetate-based adhesive in the 6-layer laminated sheet of Example 1 was changed to 75% by weight. Inventive Design Polyethylene Coated Steel Sheet Pile N
o. 4 and the designable polyethylene-coated steel sheet pile No. 4 of the present invention in which the ethylene content was changed to 98% by weight. 5 and, as a comparative example, a designable polyethylene-coated steel sheet pile No. No. 1 having the ethylene content of 40% by weight. 37, a designable polyethylene-coated steel sheet pile No. No. 37 having the ethylene content of 99% by weight.
38 was produced.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results of Table 1, together with the results of the exposure test of the designable polyethylene-coated steel sheet pile of the present invention described in Table 1 of Example 1, ethylene-acetic acid was added to the vinyl acetate adhesive layer of the present invention. When a vinyl copolymer is used, it does not cause discoloration of the printed pattern and peeling of the coating, and is good only when the ethylene content is in the range of 50 to 98% by weight.

However, when the amount of ethylene added is less than 50% by weight or more than 98% by weight, the coating peels off.

[0102]

Example 4 The vinyl acetate adhesive in the 6-layer laminated sheet of Example 1 was changed to an ethylene-vinyl acetate-vinyl chloride terpolymer, and the ethylene content in the terpolymer was changed. 45% by weight, a vinyl acetate content of 50% by weight, and a vinyl chloride content of 5% by weight. 6, the designable polyethylene-coated steel sheet pile No. 6 of the present invention in which the ethylene content in the terpolymer is 65% by weight, the vinyl acetate content is 25% by weight, and the vinyl chloride content is 10% by weight. 7. The designable polyethylene-coated steel sheet pile No. 7 of the present invention in which the ethylene content in the terpolymer was 70% by weight, the vinyl acetate content was 2% by weight, and the vinyl chloride content was 28% by weight. 8, and as a comparative example, the ethylene content in the terpolymer was 30% by weight, the vinyl acetate content was 50% by weight, and the vinyl chloride content was 20%.
Weight-designed polyethylene coated steel sheet pile No. Three
9, the ethylene content in the terpolymer is 80% by weight,
Vinyl acetate content 2% by weight, vinyl chloride content 18
Weight-designed polyethylene coated steel sheet pile No. Four
0, the ethylene content in the terpolymer is 70% by weight,
Vinyl acetate content of 1% by weight, vinyl chloride content of 29
Weight-designed polyethylene coated steel sheet pile No. Four
1, the ethylene content in the terpolymer is 40% by weight,
Vinyl acetate content 55% by weight, vinyl chloride content 5
Weight-designed polyethylene coated steel sheet pile No. Four
2, the ethylene content in the terpolymer is 49% by weight,
Vinyl acetate content 50% by weight, vinyl chloride content 1
Weight-designed polyethylene coated steel sheet pile No. Four
3, the ethylene content in the terpolymer is 68% by weight,
Vinyl acetate content 2% by weight, vinyl chloride content 30
Weight-designed polyethylene coated steel sheet pile No. 44
Was manufactured.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results shown in Table 1, when the ethylene-vinyl acetate-vinyl chloride terpolymer is used in the vinyl acetate adhesive layer of the present invention, the ethylene content is 45 to 70% by weight.
Then, only when the vinyl acetate content is 2 to 50% by weight and the vinyl chloride content is in the range of 5 to 28% by weight, there is no peeling of the coating, which is good.

[0106]

Example 5 The vinyl acetate adhesive in the 6-layer laminated sheet of Example 1 was changed to an ethylene-vinyl acetate-acrylic acid terpolymer, and the ethylene content in the terpolymer was changed. 45% by weight, a vinyl acetate content of 50% by weight, and an acrylic acid content of 5% by weight. 9. The polyethylene-coated steel sheet pile No. 9 of the present invention having an ethylene content of 65% by weight, a vinyl acetate content of 25% by weight, and an acrylic acid content of 10% by weight in the terpolymer. 10, the polyethylene-coated steel sheet pile No. 10 of the present invention having an ethylene content of 70% by weight, a vinyl acetate content of 2% by weight, and an acrylic acid content of 28% by weight in the terpolymer. 11, and as a comparative example, the ethylene content in the terpolymer was 30% by weight,
Vinyl acetate content 50% by weight, acrylic acid content 2
0% by weight of the designable polyethylene-coated steel sheet pile No. Four
5, the ethylene content of the terpolymer is 80% by weight,
Vinyl acetate content 2% by weight, acrylic acid content 18
Weight-designed polyethylene coated steel sheet pile No. Four
6, the ethylene content of the terpolymer is 70% by weight,
Vinyl acetate content 1% by weight, acrylic acid content 29
Weight-designed polyethylene coated steel sheet pile No. Four
7, the ethylene content in the terpolymer is 40% by weight,
Vinyl acetate content 55% by weight, acrylic acid content 5
Weight-designed polyethylene coated steel sheet pile No. Four
8, the ethylene content in the terpolymer is 49% by weight,
Vinyl acetate content 50% by weight, acrylic acid content 1
Weight-designed polyethylene coated steel sheet pile No. Four
9, the ethylene content in the terpolymer is 68% by weight,
Vinyl acetate content 2% by weight, acrylic acid content 30
Weight-designed polyethylene coated steel sheet pile No. Fifty
Was manufactured.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

After exposure, Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating.

From the results shown in Table 1, when the ethylene-vinyl acetate-acrylic acid terpolymer is used in the vinyl acetate adhesive layer of the present invention, the ethylene content is 45 to 70% by weight.
Then, only when the vinyl acetate content is 2 to 50% by weight and the acrylic acid content is in the range of 5 to 28% by weight, there is no peeling of the coating, which is good.

[0110]

Example 6 The vinyl acetate adhesive in the 6-layer laminated sheet of Example 1 was changed to an ethylene-vinyl acetate-methacrylic acid terpolymer, and the ethylene content in the terpolymer was changed. 45% by weight, a vinyl acetate content of 50% by weight, and a methacrylic acid content of 5% by weight. No. 12, the polyethylene-coated steel sheet pile No. of the present invention having an ethylene content of 65% by weight, a vinyl acetate content of 25% by weight, and a methacrylic acid content of 10% by weight in the terpolymer. No. 13, the polyethylene-coated steel sheet pile No. 3 of the present invention in which the ethylene content in the terpolymer was 70% by weight, the vinyl acetate content was 2% by weight, and the methacrylic acid content was 28% by weight. 14, and as a comparative example, the ethylene content in the terpolymer was 3
0% by weight, a vinyl acetate content of 50% by weight, and a methacrylic acid content of 20% by weight. No. 51, designed polyethylene-coated steel sheet pile No. 51 having an ethylene content of 80% by weight, a vinyl acetate content of 2% by weight, and a methacrylic acid content of 18% by weight in the terpolymer. No. 52, designed polyethylene-coated steel sheet pile No. 52 having an ethylene content of 70% by weight, a vinyl acetate content of 1% by weight, and a methacrylic acid content of 29% by weight in the terpolymer. 53, a design polyethylene-coated steel sheet pile No. No. 53 having an ethylene content of 40% by weight, a vinyl acetate content of 55% by weight, and a methacrylic acid content of 5% by weight in the terpolymer. 54, a design polyethylene coated steel sheet pile No. No. 54 having an ethylene content of 49% by weight, a vinyl acetate content of 50% by weight and a methacrylic acid content of 1% by weight in the terpolymer. 55, a design polyethylene coated steel sheet pile No. No. 55 having an ethylene content of 68% by weight, a vinyl acetate content of 2% by weight and a methacrylic acid content of 30% by weight in the terpolymer. 56 was produced.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results shown in Table 1, when an ethylene-vinyl acetate-methacrylic acid terpolymer is used in the vinyl acetate adhesive layer of the present invention, the ethylene content is 45 to 70% by weight and the vinyl acetate content is Only when the amount is 2 to 50% by weight and the methacrylic acid content is in the range of 5 to 28% by weight, there is no peeling of the coating, which is good.

[0114]

Example 7 The design polyethylene of the present invention in which the addition amount of IRGANOX 1076 and the addition amount of TINUVIN-P in polyvinyl chloride of the printing support film of the 6-layer laminated sheet of Example 1 were 1% by weight. Coated steel sheet pile No.
15, the addition amount of the IRGANOX 1076 is 3% by weight,
The designable polyethylene-coated steel sheet pile No. 3 of the present invention in which the amount of TINUVIN-P added was 3% by weight. 16 and, as a comparative example, without adding the IRGANOX 1076, TIN
Designed polyethylene-coated steel sheet pile No. 1 with 0.1% by weight of UVIN-P added. 57, the IRGANOX10
0.1% by weight of the additive amount of 76, a design polyethylene-coated steel sheet pile No. No. added with TINUVIN-P. 58, the addition amount of the IRGANOX 1076 was 4% by weight, TINU
Designed polyethylene-coated steel sheet pile No. 4 with the addition amount of VIN-P being 4% by weight. 59 was produced.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

After the exposure, Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating.

From the results of Table 1, together with the results of the designable polyethylene-coated steel sheet pile of the present invention in Table 1, the antioxidant of the printing support film of the present invention is in the range of 0.1 to 3% by weight, Moreover, only when the ultraviolet absorber is added in the range of 0.1 to 3% by weight, there is no fading of the printed pattern and peeling of the coating, which is excellent.

[0118]

EXAMPLE 8 IRGANOX 1076 in polyvinyl chloride of the print support film of the 6-layer laminated sheet of Example 1
RGANOX1010 (addition amount of 0.1% by weight) was changed to the designable polyethylene-coated steel sheet pile No. of the present invention. 17,
TINUVIN-P in polyvinyl chloride of the printing support film of the six-layer laminated sheet of Example 1 was replaced with TINUVIN21.
No. 3 (the addition amount is 0.1% by weight), which is the designable polyethylene-coated steel sheet pile No. 3 of the present invention. 18 was produced.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results shown in Table 1, even if the antioxidant and the ultraviolet absorber of the printing support film of the present invention are changed, if both are added in combination, it is favorable without fading of the printed pattern and peeling of the coating.

[0122]

Example 9 The resin of the printing support film of the 6-layer laminated sheet of Example 1 was changed to polyethylene terephthalate (however, the types and amounts of the antioxidant and the ultraviolet absorber remained the same), and the design polyethylene of the present invention was used. Coated steel sheet pile No.
19 was produced.

This coated steel sheet pile was cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

After exposure, Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating.

From the results shown in Table 1, even when polyethylene terephthalate is used in the printing support film of the present invention, the printed pattern is not discolored and the coating is not peeled off.

[0126]

[Embodiment 10] The designable polyethylene-coated steel sheet pile No. 3 of the present invention in which the amount of TINUVIN-P added to the transparent acrylic resin film of the 6-layer laminated sheet of Example 1 was changed to 2% by weight. 20, the designable polyethylene-coated steel sheet pile N of the present invention in which the amount of TINUVIN-P added is changed to 5% by weight
o. 21 and, as a comparative example, a designable polyethylene-coated steel sheet pile No. 3 in which the TINUVIN-P was not added. 6
0, the amount of the TINUVIN-P added was 6% by weight, and the design polyethylene coated steel sheet pile No. 61 was produced.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

After the exposure, Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating.

From the results shown in Table 1, the designable polyethylene-coated steel sheet pile No. 1 of the present invention shown in Table 1 is obtained. Combined with the result of 1, the transparent acrylic resin film of the present invention is good without fading of the printed pattern and peeling of the coating only when the ultraviolet absorber is added in the range of 0.2 to 5% by weight.

[0130]

[Embodiment 11] The UV absorber added to the transparent acrylic resin film of the six-layer laminated sheet of Embodiment 1 is TINUVI.
N213 instead of the designable polyethylene-coated steel sheet pile No. 22 was produced.

This coated steel sheet pile was cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

After the exposure, Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating.

From the results shown in Table 1, even if the ultraviolet absorbent of the transparent acrylic resin film of the present invention is changed to TINUVIN213, the printed pattern is not faded and the coating is not peeled off, which is excellent.

[0134]

Example 12 The resin of the transparent acrylic resin film of the six-layer laminated sheet of Example 1 was changed to a methyl methacrylate-vinylidene fluoride copolymer (however, the kind and the addition amount of the ultraviolet absorber were unchanged). Designable polyethylene coated steel sheet pile No. No. 23 and the resin of the transparent acrylic resin film were changed to a methyl methacrylate-ethylene-vinylidene fluoride terpolymer (however, the type and the amount of the ultraviolet absorber remained unchanged), and the design polyethylene coated steel sheet pile No. of the present invention was used. ． 24 was produced.

This coated steel sheet pile was cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results shown in Table 1, the resin of the transparent acrylic resin film of the present invention was selected from methyl methacrylate-vinylidene fluoride copolymer or methyl methacrylate-ethylene-
Even if the vinylidene fluoride terpolymer is changed to a good one, the printed pattern does not fade and the coating does not peel off.

[0138]

[Embodiment 13] The designable polyethylene-coated steel sheet pile N of the present invention in which the resin type of the transparent fluororesin film of the six-layer laminated sheet of Embodiment 1 is changed to polytetrafluoroethylene.
o. 25, the designable polyethylene-coated steel sheet pile No. of the present invention in which the resin is changed to polyvinyl fluoride. 26, the designable polyethylene-coated steel sheet pile No. of the present invention in which the resin was changed to a tetrafluoroethylene-hexafluoropropylene copolymer. 27, the designable polyethylene-coated steel sheet pile No. of the present invention in which the resin is changed to an ethylene-tetrafluoroethylene copolymer. 28, the designable polyethylene-coated steel sheet pile No. of the present invention in which the resin is changed to vinylidene fluoride-hexafluoropropylene copolymer. 29 was produced.

These coated steel sheet piles were cut into a length of 1 m and subjected to the same river exposure test as in Example 1.

Table 1 shows the results of examining the presence or absence of fading of the stone wall pattern and the presence or absence of peeling of the coating after the exposure.

From the results shown in Table 1, the resin of the transparent fluororesin film of the present invention was selected from polytetrafluoroethylene, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer or fluorine. Even if the vinylidene chloride-hexafluoropropylene copolymer is used, the printed pattern does not fade and the coating is not peeled off.

[0142]

[Embodiment 14] First, the printing support film 7 obtained by T-die extrusion molding was applied to the impression cylinder 1 using a gravure printing machine as shown in FIG.
The printed pattern layer 8 was printed on the surface of the printing support film 7 with the ink 13 inserted between the plate cylinder 12 engraved with the photograph pattern of 1 and granite, and the printed pattern sheet 14 was prepared.

Next, as shown in FIG. 10, the transparent fluororesin and the transparent acrylic resin are supplied from the extruders 15 and 16 to the two-layer T die 17 and extruded. The layered molten sheet was extruded and laminated so that the transparent acrylic resin film 9 of the two-layered sheet and the printed pattern layer 8 of the printed pattern sheet 14 were laminated together to obtain a four-layer laminated sheet 18.

On the back surface of this 4-layer laminated sheet, that is, the surface of the printing support film, the vinyl acetate adhesive 6 is extruded from the single-layer T die in a molten sheet and laminated to form a 5-layer laminated film 32 (see FIG. 1). ) Was manufactured. The composition of the 5-layer laminated film is shown below.

Vinyl acetate adhesive layer Resin: ethylene-vinyl acetate copolymer (ethylene content: 50% by weight) Film thickness: 20 μm

Printing support film Resin: Polyethylene terephthalate Antioxidant: IRGANOX1 manufactured by Ciba-Geigy Japan
076 Antioxidant addition amount: 0.5 wt% UV absorber: TINUVIN manufactured by Ciba-Geigy Japan
-P UV absorber addition amount: 0.5% by weight Film thickness: 150 μm

Pattern printing layer Ink: Fluorine-based ink Thickness: 8 μm

Transparent acrylic resin film Resin: Polymethylmethacrylate UV absorber: TINUVIN manufactured by Ciba-Geigy Japan
-P UV absorber addition amount: 2% by weight Thickness: 30 μm

Transparent fluororesin film Resin: Polyvinylidene fluoride Thickness: 30 μm

Next, a steel pipe (SGP outer diameter 200 A × length 5
The outer surface of (m) is treated by grit blasting while rotating in a spiral shape, and the surface of the surface is chromate-treated with a brush so that the total amount of chromium adhered is 500 mg / m ² , and heated to 160 ° C and baked. Further, an epoxy primer was spray-coated on the surface so as to have a film thickness of 50 μm, and was cured to be subjected to a base treatment.

Then, its surface was extrusion-coated from a maleic anhydride-modified polyethylene adhesive and a black polyethylene (the amount of carbon black added was 2.5%) T-die.

Then, the above-mentioned five-layer laminated film was pressure-bonded on the surface with a roll to cover it, and the decorative polyethylene-coated steel pipe pile No. I got 30.

The results of subjecting the coated steel pipe pile to the same river exposure test as in Example 1 are shown in Table 1.

From the results shown in Table 1, the designable polyethylene-coated steel pipe pile of the present invention is excellent without fading of the pattern or peeling of the coating even after the river exposure test for 3 years.

[0155]

Example 15 H-shaped steel (125 mm in height × 12 in side length)
The surface of 5 mm x maximum thickness 9 mm) was sandblasted to remove rust, and a chromate treatment agent was applied to the surface so that the total amount of chromium deposited would be 600 mg / m ² , and heated at 160 ° C and baked.

Epoxy primer was spray coated on the surface of the chromate-treated H-section steel to a film thickness of 50 μm,
Cured.

Then, a powder of a maleic anhydride-modified ethylene-1-butene copolymer adhesive was sprayed on the surface so that the film thickness was 400 μ, and the film thickness was 1 mm on the surface.
Powder of black ethylene-1-butene copolymer (addition amount of carbon black: 2.5%) was sprayed so that

Then, the five-layer laminated film of Example 14 was pressure-bonded to the surface with a roll, and the decorative ethylene of the present invention was formed.
Butene-1 copolymer coated H-section steel No. 31 was produced.

Table 1 shows the results of subjecting this design ethylene-1-butene copolymer-coated H-section steel to a length of 1 m and subjecting it to the same river exposure test as in Example 1.

From the results shown in Table 1, the design ethylene-1-butene copolymer-coated H-section steel of the present invention is excellent without fading of the pattern or peeling of the coating even after the river exposure test for 3 years.

[0161]

[Table 1]

[0162]

[Table 2]

[0163]

[Table 3]

[0164]

[Table 4]

[0165]

According to the present invention, as is apparent from the above examples, the surface of the steel material subjected to the base treatment is bonded with the black polyolefin containing carbon black through the modified polyolefin adhesive layer. In addition, a vinyl acetate adhesive layer, a printing support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, a transparent acrylic resin film and a transparent fluororesin film containing an ultraviolet absorber. By sequentially stacking the above, compared with the conventional design polyolefin-coated steel material, an excellent effect of preventing discoloration and peeling of the printed pattern layer even when actually used for a long period of time is exhibited.

[Brief description of drawings]

FIG. 1 is a black polyolefin layer, a vinyl acetate adhesive layer on the surface, a print support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and a transparent containing an ultraviolet absorber. It is sectional drawing which shows the steel plate of this invention which laminated-coated the acrylic resin film and the transparent fluororesin film.

FIG. 2 contains a black polyolefin layer, a vinyl acetate adhesive layer, a print support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and an ultraviolet absorber on the mountain surface. It is sectional drawing which shows the steel sheet pile of this invention which laminated | stacked and covered the transparent acrylic resin film and the transparent fluororesin film.

FIG. 3 contains a black polyolefin layer, a vinyl acetate adhesive layer, a printing support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and an ultraviolet absorber on the valley surface. It is sectional drawing which shows the steel sheet pile of this invention which laminated | stacked and covered the transparent acrylic resin film and the transparent fluororesin film.

FIG. 4 is a transparent surface having a black polyolefin layer, a vinyl acetate adhesive layer, a print support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and an ultraviolet absorber on the surface. It is sectional drawing which shows the H-section steel of this invention which laminated-coated the acrylic resin film and the transparent fluororesin film.

FIG. 5 contains a black polyolefin layer, a vinyl acetate adhesive layer, a print support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and an ultraviolet absorber on one surface. FIG. 3 is a cross-sectional view showing a structural steel for a continuous wall of the present invention in which a transparent acrylic resin film and a transparent fluororesin film are laminated and covered.

FIG. 6 is a black polyolefin layer on the outer surface, a vinyl acetate adhesive layer, a print support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and a transparent containing an ultraviolet absorber. It is sectional drawing which shows the steel pipe pile of this invention which laminated and coat | covered the acrylic resin film and the transparent fluororesin film.

FIG. 7: Black polyolefin layer on outer surface, vinyl acetate adhesive layer, printing support film made of polyvinyl chloride or polyethylene terephthalate containing antioxidant and ultraviolet absorber, printed pattern layer, transparent containing ultraviolet absorber It is sectional drawing which shows the square steel pipe pile of this invention which laminated-coated the acrylic resin film and the transparent fluororesin film.

FIG. 8: A black polyolefin layer, a vinyl acetate adhesive layer, a print support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, and a transparent ultraviolet absorber on the outer surface. It is sectional drawing which shows the steel pipe sheet pile of this invention which laminated-coated the acrylic resin film and the transparent fluororesin film.

FIG. 9 is an explanatory diagram showing an example of a method of gravure printing on the surface of the printing support film of the present invention.

FIG. 10: A printing support film made of polyvinyl chloride or polyethylene terephthalate containing an antioxidant and an ultraviolet absorber, a printed pattern layer, a transparent acrylic resin film containing an ultraviolet absorber and a transparent fluororesin film are laminated to form 4 It is explanatory drawing which shows an example of the method of manufacturing a layer laminated film.

11 is a schematic view showing that the four-layer laminated film of FIG. 10 and the black polyolefin layer are laminated with a vinyl acetate-based adhesive to form 6
It is explanatory drawing which shows an example of the method of manufacturing a layer lamination laminated sheet.

FIG. 12 is an explanatory diagram showing an example of a method of coating the mountain surface of the steel sheet pile with a 6-layer laminated laminate sheet manufactured by the method shown in FIG. 11 or the like.

FIG. 13 is an explanatory diagram showing an example of a method of coating the valley surface of the steel sheet pile with a 6-layer laminated laminate sheet manufactured by the method shown in FIG. 11 or the like.

[Explanation of symbols]

1 Steel materials such as blasted steel sheet, steel sheet pile, H-section steel, shaped steel for wall, steel pipe pile, square steel pipe pile, and steel pipe sheet pile 2 Chromate coating 3 Epoxy primer coating 4 Modified polyolefin adhesive layer 5 Black polyolefin layer 6 Vinyl Acetate Adhesive Layer 7 Printing Support Film Made of Polyvinyl Chloride or Polyethylene Terephthalate Having Antioxidant and Ultraviolet Absorber 8 Printed Pattern Layer 9 Transparent Acrylic Resin Film with Ultraviolet Absorber 10 Transparent Fluorine Resin Film 11 Gravure Printing Machine impression cylinder 12 engraving machine for gravure printing machine 13 printing ink 14 laminated film of printing pattern layer and printing support film 15 transparent fluororesin extruder 16 transparent acrylic resin extruder 17 two-layer T-die 18 printing support film, printing Pattern layer, transparent acrylic resin film and transparent fluororesin 4-layer laminate film 19 monolayer T-die 20 black polyolefin layer of Irumu, vinyl acetate adhesive layer,
Printing support film, printed pattern layer, 6-layer laminated sheet of transparent acrylic resin film and transparent fluororesin film 21 Transport roll 22 Transport table 23 Web part pressure roll 24 Auxiliary roll 25 Flange pressure roll 26 Flange pressure roll 27 Web pressure bond Roll 28 Auxiliary Roll 29 Flange Crimping Roll 30 Flange Crimping Roll 31 Claw Crimping Roll 32 Vinyl Acetate Adhesive Layer, Printing Support Film, Printed Pattern Layer, 5-Layer Laminated Film of Transparent Acrylic Resin Film and Transparent Fluorine Resin Film 33 Gravure printing machine blade

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B32B 27/20 Z 6122-4F 27/30 A 8115-4F D 8115-4F 101 8115-4F 102 8115 -4F 27/36 7016-4F

Claims (1)

[Claims] 1. A vinyl acetate-based adhesive layer, an antioxidant and an ultraviolet absorber are provided on the surface of a steel material that has been subjected to a base treatment and a black polyolefin containing carbon black is adhered to the surface of the steel material through a modified polyolefin adhesive layer. A designable polyolefin-coated steel material comprising a print supporting film containing polyvinyl chloride or polyethylene terephthalate contained therein, a print pattern layer, a transparent acrylic resin film containing an ultraviolet absorber and a transparent fluororesin film, which are successively laminated.