JP3056376B2 - Non-flammable polyvinyl chloride coated steel sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-combustible polyvinyl chloride coated steel sheet, and more particularly to a non-combustible polyvinyl chloride coated steel sheet applicable to the field of building materials for fire prevention.

[0002]

2. Description of the Related Art A polyvinyl chloride coated steel sheet is a metal sheet coated with a polyvinyl chloride film via an adhesive, and is excellent in weather resistance, corrosion resistance, workability, and design. It is widely used in the fields of home appliances, automobiles, containers, sundries, furniture and the like. The polyvinyl chloride coated steel sheet is highly evaluated for its design because it is thicker than a normal coated steel sheet and can emboss the polyvinyl chloride film. When a polyvinyl chloride-coated steel sheet is used for a building material, for example, a door material, an interior material, a roof material, etc., nonflammability may be required. In this case, it is necessary to certify the noncombustible materials specified in Article 2, Item 9 of the Building Standards Act.

[0003] Since polyvinyl chloride resin itself is flame-retardant, polyvinyl chloride-coated steel sheets having a polyvinyl chloride film thickness of 100 µm or less are subject to the Building Standard Law 2
It has passed the test specified in Article 9 and has received general certification as Noncombustible No. 1051.

However, when the thickness of the polyvinyl chloride film is 100 μm, deep embossing does not occur, so that the design is restricted, and in order to obtain the excellent embossing characteristic which is characteristic of the polyvinyl chloride coated steel sheet, the polyvinyl chloride film must be coated. The thickness is 1
It must be at least 00 μm. Therefore, in the field of building materials and the like, there is a strong demand for a polyvinyl chloride-coated steel sheet having both nonflammability and good embossability, that is, design. In addition, the thickness of the steel sheet affects the combustion test stipulated in Article 2, Item 9 of the Building Standards Act. It is a disadvantageous condition for sex. The thickness of the steel sheet of the polyvinyl chloride coated steel sheet used in the field of building materials and the like is usually 0.5 to 1.
6 mm, and nonflammability in this range is strongly required.

[0005] When the embossability is improved by setting the thickness of the polyvinyl chloride film of the ordinary polyvinyl chloride coated steel sheet to 100 µm or more, it passes the base material test and the surface test specified in Article 2, Item 9 of the Building Standards Act. Can not do. In addition, if the amount of plasticizer in the polyvinyl chloride film is simply reduced, the combustion test passes, but cracking of the polyvinyl chloride film occurs during molding and the workability is significantly reduced.
The properties as a precoated steel sheet are impaired.

Conventionally, methods for imparting nonflammability to polyvinyl chloride resins include flame retardants such as antimony oxides, metal hydroxides and metal borates, and fillers such as calcium carbonate, calcium silicate, talc and mica. Has been attempted, and for example, there are proposals in JP-A-57-47340 and JP-A-57-54054.

However, polyvinyl chloride resins containing these flame retardants and fillers are excellent in nonflammability. However, when used for polyvinyl chloride coated steel sheets, the processed part of the film becomes white during molding and the Remarkable decline in sex,
The coating becomes brittle. Therefore, it is difficult to obtain a polyvinyl chloride-coated steel sheet having both incombustibility and good embossability, that is, design, simply by blending a flame retardant and a filler into the polyvinyl chloride film.

On the other hand, when a polyvinyl chloride-coated steel sheet is used as an interior building material for fire prevention, the coating may be required to have high stain resistance, solvent resistance, or aesthetic appearance. However, since the polyvinyl chloride film contains a plasticizer, these characteristics are inferior to those of other coated steel sheets, and thus need to be improved.

[0009]

When a conventional polyvinyl chloride steel sheet is used as a non-combustible material, the thickness of the polyvinyl chloride film needs to be 100 μm or less. There is a limit. In addition, when simply reducing the amount of plasticizer in the polyvinyl chloride film or adding a flame retardant or filler to make the film thickness 100 μm or more, the incombustibility is improved, but the processability during molding is remarkable. Inferior, the function as a pre-coated steel sheet is lost.
Therefore, a polyvinyl chloride coated steel sheet having both nonflammability, designability and workability is required. Also, when polyvinyl chloride coated steel sheet is used as an interior building material for fire protection,
It is necessary to improve the stain resistance and solvent resistance of the film.

[0010]

SUMMARY OF THE INVENTION According to the present invention, a first layer of polyvinyl chloride resin is provided on a steel sheet via an adhesive.
A polyvinyl chloride film having a thickness of 70 to 150 μm in which 70 to 100 parts by weight of calcium carbonate is blended with respect to parts by weight;
Furthermore, as a second layer, a film thickness of 30 to 1 containing 15 to 25 parts by weight of a plasticizer with respect to 100 parts by weight of polyvinyl chloride.
It has a polyvinyl chloride film of 50 μm, and the total thickness of the first and second layers of the polyvinyl chloride film is 100 to 25.
0 μm, or 0.3 μm as a third layer.
Design and processing characterized by having an acrylic resin, urethane resin, polyester resin or fluorine resin film of up to 25 μm and having a printed layer between the first and second layers or between the second and third layers. The present invention relates to a nonflammable polyvinyl chloride coated steel sheet having excellent heat resistance. That is, the present invention devised a non-combustible polyvinyl chloride coated steel sheet having excellent design and workability by devising the plasticizer amount of the polyvinyl chloride film, the composition of calcium carbonate, the film thickness, and the film composition. It is. Hereinafter, the present invention will be described in detail.

The steel sheet used in the polyvinyl chloride coated steel sheet of the present invention includes cold-rolled steel sheet, cold-rolled steel sheet, zinc plating, chromium plating, tin plating, nickel plating, or alloy plating of these metals. In addition, it is possible to use a steel sheet which has been subjected to a chemical conversion treatment such as a chromate treatment, a phosphate treatment, etc., which has been subjected to a multilayer plating and the like,
It can be arbitrarily selected according to the purpose and use. Further, depending on the purpose, a stainless steel plate, an aluminum plate, a copper plate or the like can be used instead of the steel plate. Although there is no particular limitation on the thickness of the steel sheet, the thickness of the steel sheet affects the combustion test defined in Article 2, Item 9 of the Building Standards Act,
The thinner the steel plate, the more severe the conditions. Therefore, in the present invention, the thickness of the steel plate is preferably 0.5 mm or more.

As the adhesive between the steel sheet and the polyvinyl chloride film, a commonly used adhesive such as acrylic or polyester can be used. The coating amount of the adhesive is preferably 1 to 10 g / m ² .

The polyvinyl chloride resin used for the polyvinyl chloride coating may be any one produced by a production method such as suspension polymerization or emulsion polymerization. Can be used.

As plasticizers to be incorporated into the polyvinyl chloride film, generally used dioctyl phthalate, trioctyl trimellitate, triisodecyl trimellitate, dioctyl adipate, dioctyl sebacate are used. Esters, diisodecyl sebacate, dioctyl azelate, epoxidized soybean oil, epoxidized linseed oil and the like can be used. The compounding amount is 15 to 3 with respect to 100 parts by weight of polyvinyl chloride for the first layer polyvinyl chloride film.
A blend of 5 parts by weight is desirable. If the amount is less than 15 parts by weight, the processability is deteriorated, and if it is more than 35 parts by weight, the nonflammability deteriorates, which is not preferable. As for the polyvinyl chloride film of the second layer, the amount of the plasticizer is preferably 15 to 25 parts by weight based on 100 parts by weight of polyvinyl chloride. If the amount is less than 15 parts by weight, the workability deteriorates, and if it is more than 25 parts by weight, the nonflammability deteriorates, which is not preferable.

The amount of calcium carbonate to be mixed in the polyvinyl chloride film of the first layer is preferably 70 to 100 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. If the amount is less than 70 parts by weight, the incombustibility of the film is inferior, and the effect of blending is not seen.
On the other hand, if the amount is more than 100 parts by weight, the mechanical properties of the polyvinyl chloride are impaired, and the adhesion to the polyvinyl chloride film of the second layer is deteriorated during molding. Further, in addition to calcium carbonate, a small amount of a filler such as calcium silicate, talc, mica or a flame retardant such as antimony oxide, metal hydroxide, boron compound, molybdenum compound or tin oxide may be used. However, it is not preferable to mix not only calcium carbonate but also the above-mentioned filler, flame retardant and the like into the polyvinyl chloride film of the second layer, since properties such as workability and design properties are deteriorated. When a printing layer is formed between the first layer and the second layer, the second layer
The layer is desirably a transparent polyvinyl chloride film containing no coloring pigment or the like.

It is also possible to blend stabilizers, pigments, modifiers, UV absorbers, weathering aids, etc. used in the ordinary polyvinyl chloride film into the first or second layer of the polyvinyl chloride film. It is possible.

The thickness of the polyvinyl chloride film of the present invention is 70 to 150 μm for the first layer and 30 to 150 μm for the second layer.
And the total thickness of the first layer and the second layer is 100 to 25
0 μm is desirable. When the total of the thickness of the first layer and the thickness of the second layer is less than 100 μm, the embossing property is inferior. In addition, the sum of the thickness of the first layer and the thickness of the second layer is 25.
If it exceeds 0 μm, the nonflammability deteriorates, which is not preferable.
The thickness of the steel sheet affects the combustion test stipulated in Article 2, Item 9 of the Building Standards Act. When the thickness of the steel sheet exceeds 0.5 mm, the total thickness of the first and second layers is set to 250 μm or more. It is also possible.

The third layer of the present invention has a thickness of 0.3 to 2
A 5 μm acrylic resin, urethane resin, polyester resin, or fluororesin can be used. By forming these resin layers, stain resistance and solvent resistance can be improved. When the film thickness is less than 0.3 μm, the effects of these resin layers cannot be seen, and
If it exceeds 5 μm, the non-combustibility and the embossability are inferior. Further, the third layer can be applied by mixing a mixture of the above-mentioned resins or each resin according to the purpose.

Further, by forming a printing layer between the first layer and the second layer or between the second layer and the third layer according to the present invention,
The design and the appearance can be further improved. The ink used for printing is not particularly limited, but the first layer, the second layer,
Inks having excellent adhesion to the layer or the third layer are preferred. Depending on the purpose, printing of the first to fourth plates can be performed.

As the method for producing the polyvinyl chloride coated steel sheet of the present invention, any of a film laminating method, a sol method, and a method combining these two methods can be used.

In the film laminating method, two kinds of polyvinyl chloride films corresponding to the first layer and the second layer are prepared by a calendering method or an extrusion method, and prepared on a steel sheet via an adhesive layer. It is possible to laminate sequentially,
It is also possible to laminate a film in which two kinds of polyvinyl chloride films corresponding to the first layer and the second layer are bonded in advance via an adhesive layer. In this case, the surface can be embossed before or after laminating the film on the steel sheet.

In the sol method, a first layer of sol is applied on a steel sheet via an adhesive layer, gelation is performed by heating, and then a second layer of sol is applied thereon, and the gel is then heated. After embossing, it can be manufactured by embossing. Also, the first layer of sol is applied on a steel sheet via an adhesive layer, gelled by heating, and a second layer of polyvinyl chloride film is laminated thereon, followed by embossing. You can also.

In the case of forming a printing layer, after a polyvinyl chloride film is formed, it can be used in any step before or after lamination on a steel plate. Further, the formation of the third layer may be performed in any step before or after laminating the film on the steel sheet in the film method, and can be performed after the formation of the first layer and the second layer in the sol method. It is desirable to perform this before embossing.

[0024]

The present invention will be described below with reference to examples.

Examples 1 to 4 The amount of plating was 10 g / m ² and the amount of Cr was 20 mg as a post-treatment.
/ M ² of chromate - on the surface of the electro-galvanized steel sheet having a thickness of 0.5mm was subjected to preparative process, after the acrylic adhesive of heat curing type 6.4 g / m ² was applied, Gasuo - plate at Bun After baking at a temperature of 220 ° C., immediately after laminating a polyvinyl chloride film shown in Table 1, the surface is embossed (grain embossing; embossing roll surface roughness Ra =
50 μm) to produce a polyvinyl chloride coated steel sheet. In addition, the composition of Table 1 is shown by weight part.

The nonflammability, workability, whitening property and embossability were evaluated. The nonflammability and other tests were performed by the following methods.

(1) Noncombustibility The pass / fail was determined by a base material test and a surface test specified by Article 2, Item 9 of the Building Standards Act. The acceptance criteria for the substrate test and the surface test are as follows. Acceptance criteria for base material test Insert the specimen in a heating furnace with the furnace temperature adjusted between 740 ° C and 760 ° C for 20 minutes, during which the furnace temperature does not exceed the pre-insertion temperature plus 50 ° C . Pass Criteria for Surface Test After the test specimen was first heated with the sub heat source for 3 minutes, the main heat source was further added and heated for 7 minutes, and a total of 10 minutes was passed. 1) There should be no harmful deformation in fire prevention or generation of gas that is extremely harmful in evacuation. 2) Melting over the entire thickness of the specimen, a crack reaching the back of the specimen, and the width of the crack on the back is one tenth of the thickness of the entire thickness.
There is no such thing as above. 3) There should be no residual flame for at least 30 seconds after the end of heating. 4) The exhaust temperature curve of the test sample does not exceed the standard temperature curve. 5) It fuming coefficient C _A per unit area is 30 or less. [Evaluation] ○: Passed ×: Failed

(2) Workability and Whitening Property The prepared polyvinyl chloride coated steel sheet was subjected to a DuPont impact test (1 kg, 50 cm) between -5 ° C and 10 ° C to determine the degree of cracking and whitening of the film in the processed part. Evaluation was made by a five-point method. [Evaluation] 5 (good) ← → (bad) 1

(3) Embossability The embossability of the produced polyvinyl chloride-coated steel sheet was visually evaluated. [Evaluation] ○: good ×: bad

As shown in Table 2, Examples 1 to 4 of the present invention
The polyvinyl chloride coated steel sheet has a polyvinyl chloride film thickness of 100 µm or more, and has excellent workability, whitening properties, embossability and non-combustibility, and is stipulated in Article 2, Item 9 of the Building Standards Act. Passed the substrate test and surface test.

Examples 5 to 8 After applying an adhesive to the surface of an electrogalvanized steel sheet in the same manner as in Examples 1 to 4 in the same manner as in the example, baking at a sheet temperature of 220 ° C. using a gas oven. Immediately after laminating and printing the first and second layers of the polyvinyl chloride film or forming the third layer film with the structure shown in Table 3 on the upper layer, the surface is embossed (textured). Embossing; embossing roll surface roughness Ra = 50 μm) to produce a polyvinyl chloride coated steel sheet. In addition, the composition of Table 3 is shown by weight part.

The resin used for the third layer shown in Table 3 had the following structure. A: thermoplastic acrylic resin (thickness: 5 μm) B: outer layer; fluororesin (thickness: 3 μm) inner layer: acrylic resin (thickness: 2 μm) C: polyester resin (thickness: 25 μm)

The obtained polyvinyl chloride-coated steel sheet was evaluated for nonflammability, workability, whitening property and embossability in the same manner as in Examples 1-4. Further, the stain resistance and the solvent resistance were evaluated by the following methods. Stain resistance: After drawing on the film surface with oil-based magic ink (black), 24 hours later, wiping was performed with ethanol to evaluate the removability of the magic ink. [Evaluation] ○: good Δ: slightly poor ×: poor Solvent resistance: The degree of discoloration and blistering of the film surface after immersion in methyl ethyl ketone for 24 hours was evaluated. [Evaluation] ○: good △: slightly poor ×: poor

As shown in Table 4, the polyvinyl chloride coated steel sheets of Examples 5 to 8 had a polyvinyl chloride film thickness of 10
Excellent workability, whitening properties, embossability, aesthetics, stain resistance, solvent resistance, and nonflammability at 0 μm or more,
It passed the base material test and the surface test specified in Article 2, Item 9 of the Building Standards Act.

Comparative Examples 1 to 4 An adhesive was applied to the surface of an electrogalvanized steel sheet in the same manner as in the embodiment, in the same manner as in the embodiment, and baked in a gas oven at a sheet temperature of 220 ° C., and immediately Table 5
After laminating a single-layer polyvinyl chloride film shown in (1), the surface was subjected to embossing (grain embossing; embossing roll surface roughness Ra = 50 μm) to produce a polyvinyl chloride-coated steel sheet. In addition, the composition of Table 5 is shown by weight part.

The obtained polyvinyl chloride-coated steel sheet was evaluated for nonflammability, workability, whitening property and embossability in the same manner as described in Examples 1 to 4. As shown in Table 6, the polyvinyl chloride coated steel sheets of Comparative Examples 1 to 4 include:
None of them simultaneously satisfied the properties such as workability, whitening property, embossing property and noncombustibility.

[0037]

According to the present invention, the design, workability, stain resistance,
It is possible to provide a polyvinyl chloride-coated steel sheet having excellent properties such as solvent resistance and excellent incombustibility.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI E04B 1/94 E04B 1/94 V

Claims (5)

(57) [Claims] 1. A plasticizer is added as a first layer to a steel sheet by a known adhesive, with respect to 100 parts by weight of polyvinyl chloride.
A polyvinyl chloride film having a film thickness of 70 to 150 μm containing 35 to 35 parts by weight and 70 to 100 parts by weight of calcium carbonate, and a plasticizer 15 to 25 parts by weight based on 100 parts by weight of polyvinyl chloride as a second layer thereon Thickness 30-150 μm
A non-combustible polyvinyl chloride coated steel sheet having a polyvinyl chloride film of (1), wherein the total thickness of the first and second layers of the polyvinyl chloride film is 100 to 250 μm. 2. A plasticizer is added as a first layer to a steel sheet with 100 parts by weight of polyvinyl chloride via a known adhesive on a steel sheet.
A polyvinyl chloride film having a film thickness of 70 to 150 μm containing 35 to 35 parts by weight and 70 to 100 parts by weight of calcium carbonate, and a plasticizer 15 to 25 parts by weight based on 100 parts by weight of polyvinyl chloride as a second layer thereon Thickness 30-150 μm
The total thickness of the first and second layers of the polyvinyl chloride film is 100 to 250 μm, and the third layer is an acrylic resin or urethane having a thickness of 0.3 to 25 μm. Non-combustible polyvinyl chloride coated steel sheet having a resin, polyester resin or fluororesin film. 3. A plasticizer is added as a first layer to a steel sheet with 100 parts by weight of polyvinyl chloride via a known adhesive on a steel sheet.
A polyvinyl chloride film having a film thickness of 70 to 150 μm containing 35 to 35 parts by weight and 70 to 100 parts by weight of calcium carbonate, and a plasticizer 15 to 25 parts by weight based on 100 parts by weight of polyvinyl chloride as a second layer thereon Thickness 30-150 μm
A transparent polyvinyl chloride film, and the first layer and the second layer
The total thickness of the polyvinyl chloride film of the layers is 100 to 250.
A non-combustible polyvinyl chloride coated steel sheet having a thickness of μm and having a printing layer between a first layer and a second layer. 4. A plasticizer is added as a first layer to a steel sheet with 100 parts by weight of polyvinyl chloride via a known adhesive.
A polyvinyl chloride film having a film thickness of 70 to 150 μm containing 35 to 35 parts by weight and 70 to 100 parts by weight of calcium carbonate, and a plasticizer 15 to 25 parts by weight based on 100 parts by weight of polyvinyl chloride as a second layer thereon Thickness 30-150 μm
A transparent polyvinyl chloride film, and the first layer and the second layer
The total thickness of the polyvinyl chloride film of the layers is 100 to 250.
μm, having a printing layer between the first and second layers of polyvinyl chloride film, and a third layer having a thickness of 0.3 to 25.
Non-combustible polyvinyl chloride coated steel sheet having a μm acrylic resin, urethane resin, polyester resin or fluorine resin film. 5. A plasticizer is added as a first layer with a plasticizer to 100 parts by weight of polyvinyl chloride via a known adhesive on a steel sheet.
A polyvinyl chloride film having a film thickness of 70 to 150 μm containing 35 to 35 parts by weight and 70 to 100 parts by weight of calcium carbonate, and a plasticizer 15 to 25 parts by weight based on 100 parts by weight of polyvinyl chloride as a second layer thereon Thickness 30-150 μm
The total thickness of the first and second layers of the polyvinyl chloride film is 100 to 250 μm, and the third layer is an acrylic resin or urethane having a thickness of 0.3 to 25 μm. A non-combustible polyvinyl chloride coated steel sheet having a resin, polyester resin or fluororesin film and having a printed layer between a second layer and a third layer.