JPH06115004A - Polyolefin-coated steel material with design - Google Patents

Abstract

PURPOSE:To obtain a polyolefin-coated steel material with design in which the surface of a polyolefin coating has various patterns in harmony with an environment and the release of the coating and a fading by an ultraviolet light are prevented. CONSTITUTION:The surface of a steel material 1 required to have a beautiful appearance is primed. Thereon, a black polyolefin layer 5 additionally containing a carbon black, a vinyl acetate adhesive layer 6 containing a coloring pigment, an anitioxidant, and an ultraviolet light absorber, a printing pattern layer 7, and a transparent acrylic resin film 8 containing an ultraviolet light absorber, and a transparent fluororesin film 9 are laminated in order through a modified polyolefin adhesive layer 4.

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. On the surface of the adhered steel material, a specific component containing a coloring pigment, an antioxidant and an ultraviolet absorber, ethylene-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer or acrylic monomer-ethylene- It was found that the above problems can be solved by sequentially laminating a vinyl acetate-based adhesive layer made of a vinyl acetate copolymer, a printed pattern layer and a transparent acrylic resin film containing an ultraviolet absorber, and a transparent fluororesin film, and the present invention Came to.

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, color pigment, ethylene-vinyl acetate copolymer containing antioxidant and UV absorber, vinyl chloride-ethylene-
Vinyl acetate adhesive layer 6 consisting of vinyl acetate copolymer or acrylic monomer-ethylene-vinyl acetate copolymer, printed pattern layer 7 and transparent acrylic resin film 8 containing ultraviolet absorber, polytetrafluoroethylene , A polyvinylidene fluoride, polyvinyl fluoride, a tetrafluoroethylene-hexafluoropropylene copolymer, an ethylene-tetrafluoroethylene copolymer, or a transparent fluororesin film 9 made of a vinylidene fluoride-hexafluoropropylene copolymer was sequentially laminated. This is a designable polyolefin-coated 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.

When the amount of the carbon black added is less than 0.1% by weight, fading of the printed pattern cannot be prevented, and when it exceeds 5% by weight, the printed pattern layer peels off.

As the vinyl acetate adhesive 6, ethylene-vinyl acetate copolymer or ethylene, terpolymer of vinyl acetate and vinyl chloride or acrylic monomer,
A color pigment, an antioxidant and an ultraviolet absorber are used.

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, when 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 printed pattern layer. 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% and more than 28% by weight, peeling occurs between the black polyolefin coating and the printed pattern layer 7 in the river exposure test.

The ethylene-vinyl acetate copolymer or the terpolymer of ethylene, vinyl acetate and vinyl chloride, or an acrylic monomer is added to the hindered phenol system in order to prevent fading of the printed pattern layer 7. Add antioxidant and benzotriazole type UV absorber.

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

As the 2- (5-methyl-2-hydroxyphenyl) benzotriazole, TINUVIN-P manufactured by Ciba-Geigy Co., Ltd. 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 7 due to ultraviolet rays, a hindered phenol is used in an ethylene-vinyl acetate copolymer or a terpolymer of ethylene, vinyl acetate and vinyl chloride or an acrylic monomer. 0.1 to 3% by weight of a system antioxidant and 0.1 to 3% by weight of a benzooliazole type ultraviolet absorber are added.

The amount of hindered phenolic antioxidant added to the printing support film is less than 0.1% by weight, and the amount of benzotriazole ultraviolet absorber added is 0.1% by weight.
If the amount is less than 1, the fading of the printed pattern layer 7 cannot be prevented, the addition amount of the hindered phenol-based antioxidant exceeds 3% by weight and the addition amount of the benzotriazole-based ultraviolet absorber is 3% by weight.
When it goes over, the printed pattern layer 7 and the transparent acrylic resin film 8 are separated from each other.

Further, in the above ethylene-vinyl acetate copolymer or the terpolymer of ethylene, vinyl acetate and vinyl chloride or an acrylic monomer, carbon black is added to prevent the printed pattern layer 7 from fading. In addition, organic pigments such as isoindolinone yellow, quinacridone red, perinone red, phthalocyanine green and phthalocyanine blue, and inorganic pigments such as titanium oxide, chromium oxide and titanium yellow are added.

These color pigments can be colored individually or in combination of two or more in relation to the color tone of the upper printed pattern layer 7, but when the total amount of the color pigments added is in the range of 0.1 to 5% by weight. Added. When the addition amount of the coloring pigment is less than 0.1% by weight, discoloration of the printed pattern layer cannot be prevented, and when it exceeds 5% by weight, the printed pattern layer 7 is peeled off.

As the transparent acrylic resin film 8, 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.

As the ultraviolet absorber to be added, 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 the 2- (5-methyl-2-hydroxyphenyl) benzotriazole, TINUVIN-P manufactured by Ciba-Geigy Japan Ltd. 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.

If 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 9.

As the transparent fluororesin film 9, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer or vinylidene fluoride-hexafluoro. A propylene copolymer is used.

In the case of producing the designable polyolefin-coated steel material of the present invention, first, as shown in FIG. 9, a transparent acrylic resin and a transparent fluororesin are extruded from a two-layer T die 10 in two layers to form a transparent acrylic resin film 8. A laminated film 11 including two layers of the transparent fluororesin film 9 is manufactured.

Next, with a gravure printing machine as shown in FIG. 10, the above-mentioned two-layer laminated film 11 is inserted between the impression cylinder 12 and the plate cylinder 13 on which the pattern of the photograph is engraved to form the transparent acrylic resin film 8. The printed pattern layer 6 is printed on the surface with the ink 14 to form a printed pattern film 15.

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.

Next, as shown in FIG. 11, a molten film 6 of vinyl acetate adhesive is extruded from a single layer T die, and the above-mentioned printed pattern film 15 and a black polyolefin sheet are laminated to produce a five-layer laminated sheet 17. .

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 5-layer laminated sheet 17 is coated. Then, the designable polyolefin-coated steel material of the present invention is obtained.

When a black polyolefin sheet cannot be used, a vinyl acetate adhesive 6 is extruded in a sheet form from a single layer T die and laminated on the back surface of the printed pattern film 15 to form a four layer laminated film 29 (FIG. 1). To manufacture.

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 4 is sprayed with the black polyolefin resin powder to cover the black polyolefin layer 5.

Then, the above-mentioned four-layer laminated film 29 is pressure-bonded to the surface thereof to obtain the designable polyolefin-coated steel material of the present invention. From the essence of the present invention, the modified polyolefin adhesive layer 4, the black polyolefin layer 5, the vinyl acetate adhesive layer 6, the printed pattern layer 7, the transparent acrylic resin film 8 and the transparent fluororesin film 9 are formed on the surface of the coated steel material 1. It is sufficient that the layer is firmly laminated and coated, and conventionally known chromate treatment, epoxy primer, phosphate treatment, silane coupling treatment alone or 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 mountain surface, the steel sheet pile coated with the modified polyolefin adhesive layer in a molten state on the mountain surface is moved on the carrier roll 18 and the carrier table 19 as shown in FIG. The five-layer laminated sheet 17 of No. 1 is pressure-bonded by the web pressure roller 20, and then the auxiliary roller 2
1. Further, after sequentially crimping with the crimping rolls 22 and 23 of the flange portion, water cooling is performed to obtain the designable polyolefin-coated steel sheet pile (FIG. 2) of the present invention.

Further, in coating the valley surface, the steel sheet pile coated with the modified polyolefin adhesive layer in a molten state is moved on the transport roll 18 and the transport table 19 as shown in FIG. The five-layer laminated sheet 17 of No. 1 is pressure-bonded with the pressure-bonding roll 24 of the web portion, and then the auxiliary roll 2
5, the flange pressure bonding rolls 26 and 27, and the claw pressure bonding roll 28 are sequentially pressure bonded, followed by water cooling to obtain the designable 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 five-layer laminated sheet 17 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 four-layer laminated sheet 29 (FIG. 1) 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 four-layer laminated sheet 29 (FIG. 1) of the present invention is coated to obtain the designable 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.

Then, the four-layer laminated sheet 29 (FIG. 1) 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.
Next, the 4-layer laminated sheet 29 (FIG. 1) 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.

Then, the four-layer laminated sheet 29 (FIG. 1) of the present invention is pressure bonded to obtain the designable polyolefin steel pipe sheet pile of the present invention.

The designable polyolefin-coated steel material of the present invention is, as shown in FIGS. 1 to 8, a steel material 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. The scale is removed by blasting the surface, and the chromate film 2 and the epoxy primer layer 3 are sequentially laminated to perform an undercoating treatment. 5% by weight of a black polyolefin layer 5, a coloring pigment, an ethylene-vinyl acetate copolymer containing an antioxidant and an ultraviolet absorber,
Vinyl acetate adhesive layer 6 made of vinyl chloride-ethylene-vinyl acetate copolymer or acrylic monomer-ethylene-vinyl acetate copolymer, printed pattern layer 7 and transparent acrylic resin film 8 containing ultraviolet absorber , A transparent fluororesin film made of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer or vinylidene fluoride-hexafluoropropylene copolymer It is a polyolefin-coated steel material in which 9 are sequentially laminated.

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

The present invention will be described below based on examples.

[0073]

【Example】

[0074]

Example 1 First, a two-layer laminated film 11 of a transparent fluororesin film 8 and a transparent acrylic resin film 7 obtained by a two-layer T-die extrusion molding shown in FIG. The printed pattern layer 6 was printed on the surface of the transparent acrylic resin film 7 with the ink 14 inserted between the plate cylinders 13 engraved with the pattern of the photo of Ishigaki to prepare the printed pattern film 15.

On the other hand, black polyethylene was extruded from a single-layer T die to produce a black polyethylene sheet, which was cross-linked by irradiating it with an electron beam from the surface to produce an electron beam cross-linked black polyethylene sheet 4.

Then, as shown in FIG. 11, the single-layer T-die 1
A vinyl acetate adhesive 5 is extruded from 6 in the form of a molten sheet to laminate the printed pattern film 15 and the electron beam cross-linked black polyethylene sheet 5 to form a five-layer laminated sheet 17
Was manufactured. The composition of the 5-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) Pigment: Phthalocyanine blue (addition amount: 0.1% by weight) Antioxidant: manufactured by Ciba-Geigy Japan TRGANOX1
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: 30 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 mountain surface of the steel sheet pile (FSPIII type) was subjected to grit blast treatment to remove rust, and a chromate treatment agent was applied to the mountain surface so that the total amount of chromium deposited would be 500 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 heated at 190 ° C. by high frequency induction heating to cure.

Then, a powder of maleic anhydride-modified polyethylene adhesive was electrostatically coated on the surface so that the film thickness would be 250 μ, and the surface was coated with the above-mentioned five-layer laminated sheet of the present invention. The designable polyethylene-coated steel sheet pile No. of the present invention in the table. 1 was produced.

Further, as a comparative example, a design polyethylene coated steel sheet pile No. No. No. 5 coated with the above-mentioned five-layer laminated sheet of the two-layer laminated sheet lacking the transparent acrylic resin film and the transparent fluororesin film was used. 35, a designable polyethylene-coated steel sheet pile No. 3 coated with a three-layer laminated sheet lacking a transparent acrylic resin film. 36, Designed polyethylene coated steel sheet pile N coated with a three-layer laminated sheet lacking a transparent fluororesin film
o. 37 was produced.

Further, as an example of a design polyethylene-coated steel sheet pile using a conventional pattern-printed polyvinyl chloride film, first, a polyvinyl chloride film (thickness: 100 μm
A stone wall pattern was printed on the surface of m) by the gravure printing machine shown in FIG. 10 to prepare a pattern-printed polyvinyl chloride film.

Next, this pattern-printed polyvinyl chloride film was treated with the above-mentioned electron beam cross-linked black polyethylene using the above-mentioned vinyl acetate-based adhesive (however, neither coloring pigment, UV absorber nor antioxidant was added). A 4-layer laminated sheet was manufactured by laminating the sheet with the sheet.

This four-layer laminated sheet was used as the decorative polyethylene-coated steel sheet pile No. Instead of the 5-layer laminated sheet of No. 1, coated with a designable polyethylene sheet pile No. 38
Was manufactured.

Further, the designable polyethylene-coated steel sheet pile No. Instead of the 5-layer laminated sheet of No. 1, a transparent acrylic resin film (resin: polymethylmethacrylate, thickness: 50 μm) was formed on the surface of the above pattern-printed polyvinyl chloride film.
m, but no UV absorber is added, and the above-mentioned electron beam cross-linking is carried out using the above vinyl acetate adhesive (however, neither coloring pigment, UV absorber nor antioxidant is added). Designed polyethylene coated steel sheet pile No. No. coated with a 5-layer laminated sheet produced by laminating with a black polyethylene sheet. 39 was produced.

Further, the decorative polyethylene-coated steel sheet pile No. 3 of the present invention was used. Instead of the 5-layer laminated sheet of 1, a transparent fluororesin film (resin: polyvinylidene fluoride, thickness) is laminated on the surface of the above pattern-printed polyvinyl chloride film, and the above-mentioned vinyl acetate adhesive (however, a coloring pigment is used. , A UV-absorbing agent and an antioxidant were not added) was used to design a polyethylene-coated steel sheet pile No. 5 coated with a 5-layer laminated sheet produced by laminating it with the electron beam crosslinked black polyethylene sheet. 40 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, a vinyl acetate adhesive layer containing a coloring pigment, an antioxidant and an ultraviolet absorber as essential components, a printed pattern layer, and a transparent acrylic resin film containing an ultraviolet absorber as essential components. Designed polyethylene-coated steel sheet pile No. 2 laminated with a transparent fluororesin film on the surface No. 1 is a decorative polyethylene-coated steel sheet pile No. 1 lacking a transparent acrylic resin film or a transparent fluororesin film.
35-37, a designable polyethylene-coated steel sheet pile No. 3 formed by simply adhering a conventional pattern-printed polyvinyl chloride film with a vinyl acetate adhesive. 38, a designable polyethylene-coated steel sheet pile No. No. 38 in which a transparent acrylic resin film was simply laminated on the surface of the pattern-printed polyvinyl chloride film for protection. Three
9, a designable polyethylene-coated steel sheet pile No. 3 in which a transparent fluororesin film was simply laminated and protected on the surface of the pattern-printed polyvinyl chloride film. 40 is excellent in that there is no discoloration of the pattern or peeling of the coating.

[0094]

Example 2 The amount of carbon black added in the black polyethylene layer in the 5-layer laminated sheet of Example 1 of the present invention was 2.5.
The designable polyethylene-coated steel sheet pile No. of the present invention, which was changed to the weight%. 2 and the designable polyethylene-coated steel sheet pile No. 2 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. 41 and a designable polyethylene-coated steel sheet pile No. No. 41 in which the amount of carbon black added was 6% by weight. 42 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 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.

[0099]

Example 3 The ethylene content of the ethylene-vinyl acetate copolymer of the ethylene-vinyl acetate copolymer used in the vinyl acetate-based adhesive in the five-layer laminated sheet of the present invention of Example 1 was changed to 75% by weight. The modified polyethylene-coated steel sheet pile No. of the present invention. 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. 43, a designable polyethylene-coated steel sheet pile No. No. 43 having the ethylene content of 99% by weight. 44 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.

[0104]

Example 4 The vinyl acetate adhesive in the five-layer laminated sheet of the present invention of Example 1 was changed to an ethylene-vinyl acetate-vinyl chloride terpolymer, and ethylene in the terpolymer was changed. The designable polyethylene-coated steel sheet pile No. of the present invention having a content of 45% by weight, a vinyl acetate content of 50% by weight, and a vinyl chloride content of 5% by weight. 6, the ethylene content in the terpolymer is 65% by weight, the vinyl acetate content is 25
10% by weight of vinyl chloride and 10% by weight of vinyl chloride in the present invention. 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, a design polyethylene-coated steel sheet pile N having an ethylene content of 30% by weight, a vinyl acetate content of 50% by weight, and a vinyl chloride content of 20% by weight in the terpolymer.
o. 45, a design polyethylene coated steel sheet pile N having an ethylene content of 80% by weight, a vinyl acetate content of 2% by weight and a vinyl chloride content of 18% by weight in the terpolymer.
o. 46, a design polyethylene coated steel sheet pile N having an ethylene content of 70% by weight, a vinyl acetate content of 1% by weight, and a vinyl chloride content of 29% by weight in the terpolymer.
o. 47, a design polyethylene coated steel sheet pile N having an ethylene content of 40% by weight, a vinyl acetate content of 55% by weight, and a vinyl chloride content of 5% by weight in the terpolymer.
o. 42, a design polyethylene coated steel sheet pile N having an ethylene content of 49% by weight, a vinyl acetate content of 50% by weight and a vinyl chloride content of 1% by weight in the terpolymer.
o. 48, a design polyethylene coated steel sheet pile N having an ethylene content of 68% by weight, a vinyl acetate content of 2% by weight, and a vinyl chloride content of 30% by weight in the terpolymer.
o. 49 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 exposure,
Table 1 shows the results obtained by 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 an 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.

[0107]

Example 5 The vinyl acetate adhesive in the five-layer laminated sheet of the present invention of Example 1 was changed to an ethylene-vinyl acetate-acrylic acid terpolymer and the ethylene in the terpolymer was changed. The designable polyethylene-coated steel sheet pile No. 1 of the present invention having a content of 45% by weight, a vinyl acetate content of 50% by weight, and an acrylic acid content of 5% by weight. 9, the ethylene content in the terpolymer is 65% by weight, the vinyl acetate content is 25
% By weight and acrylic acid content of 10% by weight, according to the present invention. 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 3
0% by weight, a vinyl acetate content of 50% by weight, and an acrylic acid content of 20% by weight. 50, the ethylene content of the terpolymer is 8
0% by weight, a vinyl acetate content of 2% by weight, and an acrylic acid content of 18% by weight. 51, the ethylene content in the terpolymer is 70
Polyethylene coated steel sheet pile N with 1% by weight, vinyl acetate content of 1% by weight and acrylic acid content of 29% by weight
o. 52, a design polyethylene-coated steel sheet pile N having an ethylene content of 40% by weight, a vinyl acetate content of 55% by weight, and an acrylic acid content of 5% by weight in the terpolymer.
o. 53, a design polyethylene coated steel sheet pile N having an ethylene content of 49% by weight, a vinyl acetate content of 50% by weight, and an acrylic acid content of 1% by weight in the terpolymer.
o. 54, a design polyethylene coated steel sheet pile N having an ethylene content of 68% by weight, a vinyl acetate content of 2% by weight, and an acrylic acid content of 30% by weight in the terpolymer.
o. 55 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 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.

[0111]

Example 6 The vinyl acetate-based adhesive in the five-layer laminated sheet of the present invention of Example 1 was changed to an ethylene-vinyl acetate-methacrylic acid terpolymer, and ethylene in the terpolymer was changed. The decorative polyethylene-coated steel sheet pile No. of the present invention having a content of 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. 13, the ethylene content in the terpolymer is 70% by weight, the vinyl acetate content is 2% by weight, and the methacrylic acid content is 28% by weight.
Of the present invention, the decorative polyethylene coated steel sheet pile No. 1
4, and as a comparative example, a designable polyethylene-coated steel sheet pile No. 3 having an ethylene content of 30% by weight, a vinyl acetate content of 50% by weight, and a methacrylic acid content of 20% by weight in the terpolymer. 56. Designed polyethylene-coated steel sheet pile No. 56 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. 57, a design polyethylene coated steel sheet pile No. No. 57 in which the ethylene content in the terpolymer was 70% by weight, the vinyl acetate content was 1% by weight, and the methacrylic acid content was 29% by weight. 58, the ethylene content in the terpolymer is 40% by weight, the vinyl acetate content is 55% by weight,
Designed polyethylene coated steel sheet pile No. 5 having a methacrylic acid content of 5% by weight. 59, the ethylene content in the terpolymer is 49% by weight, the vinyl acetate content is 50% by weight,
Designed polyethylene coated steel sheet pile No. 1 having a methacrylic acid content of 1% by weight. No. 60, a design polyethylene coated steel sheet pile No. No. 60 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. 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, 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.

[0115]

Example 7 The design property of the present invention in which the addition amount of IRGANOX 1076 and the addition amount of TINUVIN-P in the vinyl acetate adhesive of the five-layer laminated sheet of the present invention of Example 1 were 1% by weight. Polyethylene coated steel sheet pile No. 15,
The amount of IRGANOX 1076 added was 3% by weight, and TIN
The designable polyethylene-coated steel sheet pile No. 3 of the present invention in which the amount of UVIN-P added was 3% by weight. 16, and as a comparative example, without adding the IRGANOX 1076,
Decorative polyethylene coated steel sheet pile 62 with 0.1% by weight of NP, 0.1% by weight of IRGANOX 1076 with decorative polyethylene coated steel sheet pile No. TINUVIN-P added. 63, the IRGANO
X1076 was added in an amount of 4% by weight and TINUVIN-P was added in an amount of 4% by weight. 64 was produced.

Each of the coated steel sheet piles 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 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.

[0119]

[Embodiment 8] IRGANOX 1076 in the vinyl acetate adhesive of the 5-layer laminated sheet of the present invention of Embodiment 1 is replaced with IRGA.
The designable polyethylene-coated steel sheet pile No. No. of the present invention in which NOX1010 (addition amount was 0.1% by weight) was used. 17, TINU in the vinyl acetate adhesive of the five-layer laminate sheet of Example 1
The designable polyethylene-coated steel sheet pile No. of the present invention in which VIN-P was changed to TINUVIN213 (the addition amount was 0.1% by weight). 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.

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 if the antioxidant and the ultraviolet absorber of the printing support film of the present invention are changed, if both are added in combination, the printed pattern is not discolored and the coating is not peeled off.

[0123]

Example 9 Color pigment (phthalocyanine blue) in the vinyl acetate adhesive of the 5-layer laminated sheet of the present invention of Example 1
Of the decorative polyethylene-coated steel sheet pile No. of the present invention in which the amount of addition of 2.5% by weight was changed. 19 and the phthalocyanine blue of the present invention in which the addition amount of the phthalocyanine blue was changed to 5% by weight. 20 was produced.

Further, as a comparative example, a design polyethylene coated steel sheet pile No. No. containing no phthalocyanine blue in the vinyl acetate adhesive of the five-layer laminated sheet of the present invention was added. No. 65 and the phthalocyanine blue are added in an amount of 6 wt. 66 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 1 of the present invention in Table 1, the addition amount of the color pigment in the vinyl acetate adhesive layer of the present invention is 0.
Only when the amount is in the range of 1 to 5% by weight, there is no discoloration of the printed pattern layer and no peeling of the printed pattern layer even after exposure to rivers, which is good.

[0128]

Example 10 The coloring pigment in the vinyl acetate-based adhesive of the five-layer laminated sheet of the present invention of Example 1 was changed to chromium oxide (addition amount:
3% by weight) of the present invention in which the designable polyethylene-coated steel sheet pile No. 21, the coloring pigment is chromium oxide (addition amount: 1
20% by weight) and titanium yellow (addition amount: 2% by weight), which is a modified polyethylene-coated steel sheet pile 22 of the present invention.
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, even when the amount of the coloring pigment added to the vinyl acetate adhesive layer of the present invention was changed to chromium oxide alone or a mixture of chromium oxide and titanium oxide, fading and peeling of the printed pattern layer were observed. It is good without.

[0132]

Example 11 TINUVIN-P added to the transparent acrylic resin film of the five-layer laminated sheet of the present invention of Example 1
Of the designable polyethylene-coated steel sheet pile No. of the present invention in which the addition amount of 2% by weight was changed. 23, the designable polyethylene-coated steel sheet pile No. 23 of the present invention in which the amount of TINUVIN-P added was changed to 5% by weight. 24, and the TINUVI as a comparative example
Designed polyethylene coated steel sheet pile N without addition of NP
o. 67, a designable polyethylene-coated steel sheet pile No. 68 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 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.

[0136]

[Example 12] The ultraviolet absorber added to the transparent acrylic resin film of the five-layer laminated sheet of the present invention of Example 1 was used as TI.
Instead of NUVIN 213, the designable polyethylene-coated steel sheet pile No. 25 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 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.

[0140]

Example 13 The resin of the transparent acrylic resin film of the five-layer laminated sheet of the present invention of Example 1 was methyl methacrylate
The designable polyethylene-coated steel sheet pile No. of the present invention, which was changed to a vinylidene fluoride copolymer (however, the type and amount of the ultraviolet absorber remained unchanged). No. 26 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), the designable polyethylene-coated steel sheet pile No. of the present invention ． 27 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, 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.

[0144]

[Example 14] The designable polyethylene-coated steel sheet pile No. of the present invention in which the resin type of the transparent fluororesin film of the five-layer laminated sheet of the present invention of Example 1 was changed to polytetrafluoroethylene. 28, the designable polyethylene-coated steel sheet pile No. of the present invention in which the resin is changed to polyvinyl fluoride. 29,
The design polyethylene-coated steel sheet pile No. of the present invention in which the resin is changed to a tetrafluoroethylene-hexafluoropropylene copolymer. No. 30, the designable polyethylene-coated steel sheet pile No. of the present invention in which the resin was changed to an ethylene-tetrafluoroethylene copolymer. 31, a designable polyethylene-coated steel sheet pile No. 3 of the present invention in which the resin is changed to a vinylidene fluoride-hexafluoropropylene copolymer. 32 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 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.

[0148]

Example 15 First, a two-layer laminated film 11 of a transparent fluororesin film 8 and a transparent acrylic resin film 7 obtained by a two-layer T-die extrusion molding shown in FIG. 9 and an impression cylinder 12 of a gravure printing machine shown in FIG. Plate cylinder 13 engraved with the pattern of the photo of Ishigaki
Insert the transparent acrylic resin film 7 with the ink 14
The printed pattern layer 6 is printed on the surface of the printed pattern film 15
It was created.

On the back surface of this printed pattern film, that is, the surface of the printed pattern layer 6, a vinyl acetate adhesive 5 is extruded from a single layer T die in a molten sheet and laminated to form a four-layer laminated film 9 (see FIG. 1). ) Was manufactured. The composition of the 4-layer laminated film is shown below.

Vinyl acetate adhesive layer Resin: Ethylene-vinyl acetate copolymer (ethylene content: 50% by weight) 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 Pigment: titanium oxide (addition amount: 1% by weight), chromium oxide (addition amount: 1% by weight) and carbon black (addition amount: 1% by weight) Film thickness: 20 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 four-layer laminated film was pressure-bonded to the surface by a roll to cover it, and the decorative polyethylene-coated steel pipe pile No. I got 33.

The results of subjecting this 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 good without fading of the pattern and peeling of the coating even after the river exposure test for 3 years.

[0159]

Example 16 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 60 μ,
Cured.

Then, a powder of a maleic anhydride-modified ethylene-1-butene copolymer adhesive was sprayed on the surface so that the film thickness became 350 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 four-layer laminated film of Example 15 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. 34 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 designable ethylene-1-butene copolymer-coated H-section steel of the present invention is good without fading of the pattern and peeling of the coating even after the river exposure test for 3 years.

[0165]

[Table 1]

[0166]

[Table 2]

[0167]

[Table 3]

[0168]

[Table 4]

[0169]

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. , A coloring pigment, a vinyl acetate-based adhesive layer containing an antioxidant and an ultraviolet absorber, a printed pattern layer, a transparent acrylic resin film containing a ultraviolet absorber and a transparent fluororesin film are sequentially laminated, Compared with the design polyolefin coated steel material, it exhibits an excellent effect of preventing discoloration and peeling of the printed pattern layer even after long-term actual use.

[Brief description of drawings]

FIG. 1 shows a black polyolefin layer, a coloring pigment, an antioxidant, a vinyl acetate adhesive layer containing a UV absorber, a printed pattern layer, a transparent acrylic resin film containing a UV absorber and a transparent fluorine resin film on the surface. It is sectional drawing which shows the steel plate of this invention laminated and covered.

[FIG. 2] Black polyolefin layer on the mountain surface, a vinyl acetate adhesive layer containing a coloring pigment, an antioxidant and an ultraviolet absorber, a printed pattern layer, a transparent acrylic resin film and a transparent fluororesin film containing an ultraviolet absorber It is sectional drawing which shows the steel sheet pile of this invention which laminated-coated.

[FIG. 3] A black polyolefin layer on the valley surface, a vinyl acetate adhesive layer containing a coloring pigment, an antioxidant and an ultraviolet absorber, a printed pattern layer, and a transparent acrylic resin film and a transparent fluororesin film containing an ultraviolet absorber. It is sectional drawing which shows the steel sheet pile of this invention which laminated-coated.

FIG. 4 shows a transparent acrylic resin film and a transparent fluororesin film having a black polyolefin layer, a coloring pigment, an antioxidant, a vinyl acetate adhesive layer containing a UV absorber, a printed pattern layer, and a UV absorber on the surface. It is sectional drawing which shows the H-section steel of this invention by which lamination coating was carried out.

FIG. 5: A black polyolefin layer on one surface, a vinyl acetate adhesive layer containing a coloring pigment, an antioxidant and an ultraviolet absorber, a printed pattern layer, a transparent acrylic resin film and a transparent fluororesin film containing an ultraviolet absorber. FIG. 3 is a cross-sectional view showing a shaped steel for wall connection of the present invention in which the above is laminated and coated.

FIG. 6 shows a black polyolefin layer, a coloring pigment, an antioxidant, a vinyl acetate adhesive layer containing a UV absorber, a printed pattern layer, a transparent acrylic resin film containing a UV absorber and a transparent fluorine resin film on the outer surface. It is sectional drawing which shows the steel pipe pile of this invention which laminated and coat | covered.

FIG. 7 shows a black polyolefin layer, a coloring pigment, an antioxidant, a vinyl acetate-based adhesive layer containing an ultraviolet absorber, a printed pattern layer, and a transparent acrylic resin film and a transparent fluororesin film containing an ultraviolet absorber on the outer surface. It is sectional drawing which shows the square steel pipe pile of this invention which laminated and coat | covered.

[FIG. 8] A transparent acrylic resin film and a transparent fluororesin film having a black polyolefin layer, a coloring pigment, an antioxidant, a vinyl acetate adhesive layer containing a UV absorber, a printed pattern layer, and a UV absorber on the outer surface. It is sectional drawing which shows the steel pipe sheet pile of this invention by which lamination coating was carried out.

FIG. 9 is an explanatory view showing an example of a method for producing a two-layer laminated film of a transparent fluororesin film and a transparent acrylic resin film of the present invention.

FIG. 10: Photographic printing is performed on the transparent acrylic film side of the two-layer laminated film of the transparent fluororesin film and the transparent acrylic resin film of the present invention by a gravure printing machine, and the transparent fluororesin film, the transparent acrylic resin film and the printed pattern layer Explanatory drawing which shows the method of manufacturing the 3-layer laminated film of FIG.

11 is a cross-sectional view showing that the three-layer laminated film of FIG. 10 and the black polyolefin layer are laminated with a vinyl acetate-based adhesive to form 5
It is explanatory drawing which shows an example of the method of manufacturing a layer 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 5-layer laminated sheet produced 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 a steel sheet pile with a 5-layer laminated sheet produced by the method shown in FIG. 11 or the like.

[Explanation of symbols]

1 Steel materials such as blasted steel plate, steel sheet pile, H-section steel, shaped steel for wall, steel pipe pile, square steel pipe pile, steel pipe sheet pile, etc. 2 Chromate coating 3 Epoxy primer coating 4 Modified polyolefin adhesive layer 5 Black polyolefin layer 6 Vinyl acetate adhesive layer having color pigment, antioxidant and UV absorber 7 Printed pattern layer 8 Transparent acrylic resin film with UV absorber 9 Transparent fluororesin film 10 Two-layer T-die 11 Transparent fluororesin film and transparent Two-layer laminated sheet of acrylic resin film 12 Impressor of gravure printing machine 13 Engraver of gravure printing machine 14 Printing ink 15 Three-layer laminated film of transparent fluororesin film, transparent acrylic resin film and printed pattern layer 16 Single layer T-die 17 Transparent fluororesin film, transparent acrylic resin film, printed pattern layer, vinyl acetate Adhesive layer and 5-layer laminated sheet of black polyethylene 18 Conveying roll 19 Conveying table 20 Web part crimping roll 21 Auxiliary roll 22 Flange part crimping roll 23 Flange part crimping roll 24 Web part crimping roll 25 Auxiliary roll 26 Flange part crimping roll 27 Flange Part pressure bonding roll 28 Claw part pressure bonding roll 29 4-layer laminated film of transparent fluororesin film, transparent acrylic resin film, printed pattern layer and vinyl acetate adhesive layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B32B 27/30 A 8115-4F 102 8115-4F 33/00 7639-4F

Claims (1)

[Claims] 1. A vinyl acetate containing a coloring pigment, an antioxidant and an ultraviolet absorber on the surface of a surface-treated steel material on which a black polyolefin containing carbon black is adhered via a modified polyolefin adhesive layer. A designable polyolefin-coated steel material comprising a transparent adhesive resin film, a printed pattern layer, a transparent acrylic resin film containing an ultraviolet absorber and a transparent fluororesin film, which are sequentially laminated.