JP3034186B2 - Construction method of marking film, marking film and adhesive film for underlay - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for applying a marking film, a marking film, and an adhesive film for undercoating. More specifically, the present invention has excellent weather resistance when adhered to stainless steel and used outdoors, swells the film even after a long time, displaces the marking film, and discolors the pressure-sensitive adhesive layer. The present invention relates to a method of applying a vinyl chloride resin-based marking film, which does not cause cracks, a marking film, and an adhesive film for undercoating.

[0002]

2. Description of the Related Art A marking film is a film in which a pressure-sensitive adhesive is laminated on a printed plastic film, etc., which is easy to attach, requires no skill, and requires no drying time compared to painting. Therefore, the work time is short, the sticking work can be largely automated, and the initial adhesive force is large, the type of the adherend can be relatively selected, and it can be peeled off relatively easily when necessary. The amount of use for vehicles such as trains and automobiles, signs, and fences at construction sites is increasing year by year. As a resin for marking film,
A vinyl chloride resin having good printing characteristics and following a certain curved surface is often used, and an acrylic pressure-sensitive adhesive is often used as the pressure-sensitive adhesive. However, when a vinyl chloride resin-based marking film having a transparent or translucent portion is adhered to stainless steel and used for outdoor use, the pressure-sensitive adhesive tends to deteriorate over time, and the film may have irregularities. A phenomenon such as displacement of the marking film or discoloration of the pressure-sensitive adhesive occurs. Eventually, the marking film falls off, and the appearance of the deteriorated pressure-sensitive adhesive is contaminated. Conventionally, the deterioration of a marking film attached to a stainless steel plate for outdoor use is considered to be deterioration due to external factors such as light, heat, moisture, and oxygen, and the action of metal ions derived from the stainless steel plate. Attempts have been made to add an ultraviolet absorber or an antioxidant to the pressure-sensitive adhesive or both, or to select a material having essentially good weather resistance. But,
With such means, sufficient weather resistance cannot be obtained, and there has been a demand for the development of a vinyl chloride resin-based marking film that can be adhered to stainless steel and used outdoors.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for applying a vinyl chloride resin-based marking film which can be adhered to stainless steel and used for outdoor applications, a marking film and an adhesive film for undercoating. It was made for the purpose of.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the deterioration by providing a barrier layer made of a non-chlorine resin between the marking film and the stainless steel. It has been found that this can be prevented, and the present invention has been completed based on this finding. That is, the present invention provides (1) a method in which an adhesive film comprising a non-chlorine-based resin film and a pressure-sensitive adhesive layer is adhered to the surface of stainless steel, and a marking comprising a vinyl chloride resin film and a pressure-sensitive adhesive layer. (2) The marking film according to (1), wherein the chlorine-free resin film has a transmittance of 200% to 400 nm of 35% or less. (3) A method for applying a marking film, which comprises applying a non-chlorine-based resin to the surface of stainless steel, and then laminating a marking film comprising a vinyl chloride resin film and a pressure-sensitive adhesive layer thereon. ) Transparent or translucent vinyl chloride resin film, pressure-sensitive adhesive layer, 20
A marking film for stainless steel, comprising a laminate of a non-chlorine-based resin film having a transmittance of 0 to 400 nm of 35% or less and a pressure-sensitive adhesive layer, and
(5) For underlaying a transparent or translucent vinyl chloride resin-based marking film to be adhered to stainless steel, comprising a non-chlorine-based resin film having a transmittance of 200 to 400 nm of 35% or less and a pressure-sensitive adhesive layer. Adhesive film.

There is no particular limitation on the vinyl chloride resin marking film used in the present invention, and a known marking film having a pressure-sensitive adhesive layer provided on one side of a film of a support can be used. The film of the support can be subjected to printing or the like as necessary. The material of the pressure-sensitive adhesive is not particularly limited, for example, a rubber-based pressure-sensitive adhesive,
Acrylic pressure-sensitive adhesives and other pressure-sensitive adhesives such as polyvinyl ether and silicone can be used. Pressure-sensitive adhesives, natural rubber, synthetic isoprene rubber, reclaimed rubber, SBR, polyisobutylene, NBR, polyvinyl ether, polyacrylate, styrene-isoprene or styrene-butadiene block copolymer and other elastic bodies, polyterpenes, Rosin or a derivative thereof, oil-soluble phenol resin, coumarone-indene resin, tackifying resin such as petroleum hydrocarbon resin, mineral oil, lanolin, plasticizer such as liquid polybutene, zinc white, titanium white, calcium carbonate, clay, hydroxide It can be prepared by adding a filler such as aluminum and pigment, an antioxidant for rubber, an antioxidant such as metal dithiocarbamate and a metal chelating agent, and an ultraviolet absorber. The pressure-sensitive adhesive can be crosslinked with an epoxy compound, a metal chelate, an isocyanate-based compound, or the like, if necessary. Among these, a pressure-sensitive adhesive obtained by using an acrylic ester copolymer having a reactive functional group as an elastic body and cross-linking with an epoxy compound can be particularly preferably used.

In the method of the present invention, a barrier layer is provided between a vinyl chloride resin-based marking film and stainless steel. The barrier layer can be provided by attaching a non-chlorine-based resin film and a pressure-sensitive adhesive adhesive film to a stainless steel, or applying a non-chlorine-based resin to the surface of the stainless steel. If the support of the pressure-sensitive adhesive film serving as the barrier layer is a chlorine-based resin film such as a vinyl chloride resin, chlorine or its ions are desorbed due to photodeterioration, and diffuse through the pressure-sensitive adhesive layer to reach stainless steel. Alternatively, the ions promote ionization of the metal of stainless steel, and the catalytic action of the metal ions and light energy promotes the deterioration of the pressure-sensitive adhesive, which is not preferable. Also, when the resin applied to the stainless steel is a chlorine-based resin, the same action promotes the deterioration of the pressure-sensitive adhesive, which is not preferable. An adhesive film using a non-chlorine resin film as a support is adhered to the surface of stainless steel, or a non-chlorine resin is applied, and a marking film consisting of a vinyl chloride resin film and a pressure-sensitive adhesive layer is applied. By laminating, it is possible to prevent metal ionization and prevent deterioration of the pressure-sensitive adhesive. In the method of the present invention, the non-chlorine-based resin film of the pressure-sensitive adhesive film used as the undercoat that becomes the barrier layer preferably has a transmittance of 200 to 400 nm of 35% or less, and more preferably 20% or less. More preferred. The durability of the marking film attached to the stainless steel can be further improved by reducing the amount of light energy penetrating by concealing the ultraviolet light by the adhesive film. The transmittance of the adhesive film is 200 to 400 n of the adhesive film by a spectrophotometer.
The transmittance curve in the ultraviolet region of m is drawn, and it can be determined from the integral value.

The material of the non-chlorine resin film serving as the support of the pressure-sensitive adhesive film used for the undercoating is not particularly limited as long as it does not contain chlorine, and known non-chlorine resin films and sheets are used. be able to. Examples of such films and sheets include films and sheets of polyurethane, polyolefin, acrylic resin, fluororesin, polyester, polyamide and the like. The shape of the support is not particularly limited, and may be, for example, a single-layer film, a multilayer film, a nonwoven film, a porous film, a foamed film, or a combination thereof. The thickness of the support is preferably from 10 to 200 μm,
More preferably, it is 100 μm. The opacity can be improved by adding a pigment or the like to the support, if necessary, or by performing evaporation or the like. The pressure-sensitive adhesive of the pressure-sensitive adhesive film used in the method of the present invention is not particularly limited. For example, a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and other pressure-sensitive adhesives such as polyvinyl ether and silicone are used. be able to. Pressure-sensitive adhesives, natural rubber, synthetic isoprene rubber, reclaimed rubber, SBR, polyisobutylene, NBR, polyvinyl ether, polyacrylate, styrene-isoprene or styrene-butadiene block copolymer and other elastic bodies, polyterpenes, Rosin or a derivative thereof, oil-soluble phenol resin, coumarone-indene resin, tackifying resin such as petroleum hydrocarbon resin, mineral oil, lanolin, plasticizer such as liquid polybutene, zinc white, titanium white, calcium carbonate, clay, hydroxide It can be prepared by adding a filler such as aluminum and pigment, an antioxidant for rubber, an antioxidant such as metal dithiocarbamate and a metal chelating agent, and an ultraviolet absorber. As the pressure-sensitive adhesive, a solvent type and an emulsion type can be used. When the pressure-sensitive adhesive is of a solvent type, it can be a one-part curing type or a two-part curing type. In the case of a two-component curing type solvent-type pressure-sensitive adhesive using an acrylic ester-based elastic material,
It is preferred to use a non-yellowing type crosslinking agent. The coating amount of the pressure sensitive adhesive is preferably 5 to 80 g / m ^2, and more preferably 15 to 40 g / m ^2.

FIG. 1 is a laminated sectional view of a marking film according to the method of the present invention using an adhesive film as a barrier layer. An adhesive film composed of a non-chlorine-based resin film 2 and a pressure-sensitive adhesive layer 3 is adhered on stainless steel 1, and a marking film composed of a vinyl chloride resin film 4 and a pressure-sensitive adhesive layer 5 is further formed thereon. It is laminated. Further, in the method of the present invention, a chlorine-free resin can be applied as a barrier layer between the marking film and the stainless steel. The non-chlorine resin used as the barrier layer can be used without any particular limitation as long as it has good adhesion to stainless steel and does not easily peel off. Examples of the material for forming such a barrier layer include: Acrylic resin, urethane resin, polyester resin, ethylene-
Examples thereof include vinyl acetate copolymer resins.
One of these resins can be used alone, and 2
A mixture of more than one species can be used. There is no particular limitation on the method of forming the resin layer on the surface of stainless steel, and the resin layer can be formed by applying a resin emulsion or a solution diluted with a solvent, followed by drying, or a resin film prepared in advance. The resin layer can be formed by thermocompression bonding on the surface of stainless steel. The thickness of the resin layer formed on the surface of stainless steel is 1
It is preferably from 100 to 100 μm, and more preferably from 2 to 50 μm. The resin for forming the resin layer may be a transparent resin, an opaque resin, a colored resin, or the like.
It can be appropriately selected and used. FIG. 2 is a laminated cross-sectional view of a marking film according to the application method of the present invention using a coating resin as a barrier layer. A non-chlorine-based resin 6 having an adhesive property to the stainless steel is applied on the stainless steel 1, and a marking film composed of a vinyl chloride resin film 4 and a pressure-sensitive adhesive layer 5 is further laminated thereon. The stainless steel marking film used in the construction method of the present invention is a transparent or translucent vinyl chloride resin,
It is formed by laminating a pressure-sensitive adhesive layer, a non-chlorine-based resin film having a transmittance of 200 to 400 nm of 35% or less, and a pressure-sensitive adhesive layer. The transparent or translucent plastic film can be subjected to printing or the like as necessary. 200 to 400 nm to be a pressure-sensitive adhesive layer and a barrier layer
The material and thickness of the non-chlorine resin film having a transmittance of 35% or less can be used as described above.

[0009]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Example 1 A marking film was applied to a stainless steel plate by the method of the present invention using an adhesive film as a barrier layer. The marking film used was 35 g of an acrylic ester-based pressure-sensitive adhesive cross-linked with an epoxy-based cross-linking agent on a transparent weather-resistant polyvinyl chloride resin film having a thickness of 50 μm.
/ M ² to form a pressure-sensitive adhesive layer. Also,
The pressure-sensitive adhesive film used for the lower layer as a barrier layer is a polyester resin film having a transmittance of 29% and a thickness of 50 μm,
35g / m ^{2 of the} same pressure-sensitive adhesive as the marking film
It is applied to form a pressure-sensitive adhesive layer. Height 150mm,
After degreasing a SUS304 stainless steel plate of 70 mm in width and 3 mm in thickness, an adhesive film cut into 110 mm in length and 50 mm in width is adhered to the center of the stainless steel plate.
A test piece was prepared by laminating marking films cut to 0 mm and 50 mm in width. Using a xenon weatherometer (Ci65A type, manufactured by Atlas), the test piece was irradiated with black panel temperature 63 ± 3 ° C., relative humidity 50%, 102 minutes, followed by irradiation for 18 minutes, according to JIS B 7754. The accelerated weathering test was performed by a 120-minute cycle in which spraying was repeated. After 500 hours and 1,
The appearance of the test specimen was visually observed after 000 hours,
In each case, there was no undulation or deviation in the marking film, and no discoloration of the pressure-sensitive adhesive layer was observed. Example 2 A marking film was applied to a stainless steel plate according to the method of the present invention, using a resin layer having adhesion to stainless steel as a barrier layer. The marking film used was the same as that used in Example 1, and the resin layer was a one-component curable urethane-based resin [Natco Paint,
Megaton sealer] was used. 150mm in height, 70m in width
After a SUS304 stainless steel plate having a thickness of 3 mm and a thickness of 3 mm was degreased, the one-component curable urethane-based resin was applied to the entire surface to a thickness of 10 μm and dried. Then, in the center,
A test piece was prepared by attaching a marking film cut into a length of 110 mm and a width of 50 mm. This test piece was subjected to an accelerated weather resistance test in the same manner as in Example 1, and the appearance of the test piece was visually observed after 500 hours and 1,000 hours. After 500 hours, there was no undulation or deviation in the marking film, and no discoloration of the pressure-sensitive adhesive layer was observed. After 1,000 hours and 500 hours later, the marking film had no undulation or deviation, and no discoloration of the pressure-sensitive adhesive layer was observed. Comparative Example 1 A marking film was applied to a stainless steel plate without providing a barrier layer. The marking film used is the same as that used in Example 1. Height 150m
A SUS304 stainless steel plate having a width of 70 mm, a width of 70 mm and a thickness of 3 mm was simply degreased, and a marking film cut into a length of 110 mm and a width of 50 mm was attached to the center thereof to produce a test piece. The test piece was subjected to an accelerated weather resistance test in the same manner as in Example 1, and after 500 hours and 1,000 times.
After an hour, the appearance of the test piece was visually observed. After 500 hours, undulations and deviations occur in the marking film,
Further, the pressure-sensitive adhesive layer was discolored to brown. 1,000
After a period of time, the waviness and displacement of the marking film and the discoloration of the pressure-sensitive adhesive layer became more remarkable. Comparative Example 2 A marking film was applied to a stainless steel plate using an adhesive film having a polyvinyl chloride resin film as a support as a barrier layer. The marking film used is the same as that used in Example 1. The adhesive film used was a pressure-sensitive adhesive layer formed by applying 35 g / m ^{2 of} an acrylic ester-based pressure-sensitive adhesive cross-linked with an epoxy-based cross-linking agent to a transparent weather-resistant polyvinyl chloride resin film having a thickness of 50 μm. It is what it was. 150mm in height, 70m in width
m, after degreasing a SUS304 stainless steel plate with a thickness of 3 mm, an adhesive film cut into a length of 110 mm and a width of 50 mm is adhered to the center of the SUS304 stainless steel plate.
A test piece was prepared by laminating marking films cut to a width of 50 mm. This test piece was subjected to an accelerated weather resistance test in the same manner as in Example 1, and after 500 hours and at 1,000 hours.
After 0 hour, the appearance of the test piece was visually observed. 500
After a period of time, the marking film slightly undulated and shifted, and the pressure-sensitive adhesive layer had turned pale yellow.
After 1,000 hours, the undulation and displacement of the marking film became remarkable, and the pressure-sensitive adhesive layer turned brown. Table 1 summarizes the results of Examples 1 and 2 and Comparative Examples 1 and 2.

[0010]

[Table 1]

[Note] Film undulation ：: No film undulation is observed. Δ: The film has slightly undulated. X: The film has apparent undulation. Film misalignment フ ィ ル ム: The film remains at the first sticking position. Δ: The film is slightly displaced from the first sticking position. X: The film is clearly displaced from the first sticking position. Discoloration of pressure-sensitive adhesive ○: No discoloration is observed in the pressure-sensitive adhesive. Δ: The pressure-sensitive adhesive is slightly discolored. X: The pressure-sensitive adhesive is clearly discolored. From the results in Table 1, the transparent films of the surface layers of the marking films used in Examples 1 and 2 and Comparative Examples 1 and 2 have the same effects of external light, moisture, oxygen, heat, etc. Regardless, Examples 1 and 2 having a barrier layer made of a non-chlorine resin between a marking film and a stainless steel sheet, Comparative Example 1 having no barrier layer, and a comparison having a barrier layer of a polyvinyl chloride resin film In Example 2, a remarkable difference is observed in the undulation and displacement of the film, and the discoloration of the pressure-sensitive adhesive. This indicates that the factor of deterioration comes from the stainless steel plate side,
It was confirmed that deterioration can be prevented by providing a barrier layer made of a non-chlorine resin between the marking film and the stainless steel plate.

[0012]

According to the method for applying a marking film, the marking film and the adhesive film for underlaying of the present invention, even if the vinyl chloride resin-based marking film is adhered to stainless steel and used outdoors, pressure-sensitive adhesion can be achieved. Deterioration of the agent hardly progresses, and generation of undulation and displacement of the marking film and discoloration of the pressure-sensitive adhesive can be suppressed.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a laminated marking film according to an application method of the present invention using an adhesive film as a barrier layer.

FIG. 2 is a laminated sectional view of a marking film according to the application method of the present invention using a coating resin as a barrier layer.

[Explanation of symbols]

 Reference Signs List 1 stainless steel 2 chlorine-free resin film 3 pressure-sensitive adhesive layer 4 vinyl chloride resin film 5 pressure-sensitive adhesive layer 6 chlorine-free resin

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C09J 7/02

Claims (5)

(57) [Claims] An adhesive film comprising a chlorine-free resin film and a pressure-sensitive adhesive layer is adhered to the surface of stainless steel, and a marking film comprising a vinyl chloride resin film and a pressure-sensitive adhesive layer is laminated. A method for applying a marking film, characterized in that: 2. The non-chlorine resin film has a thickness of 200 to 400.
The method according to claim 1, wherein the transmittance of the marking film is 35% or less. 3. A method for applying a marking film, comprising applying a chlorine-free resin to the surface of stainless steel, and then laminating a marking film comprising a vinyl chloride resin film and a pressure-sensitive adhesive layer thereon. 4. A transparent or translucent vinyl chloride resin film, a pressure-sensitive adhesive layer, and a transmittance of 200 to 400 nm of 35.
% Of a non-chlorine-based resin film and a pressure-sensitive adhesive layer, each of which is less than 0.1%. 5. A pressure-sensitive adhesive layer comprising a chlorine-free resin film having a transmittance of 200 to 400 nm of 35% or less and a pressure-sensitive adhesive layer.
Adhesive film for undercoating of transparent or translucent vinyl chloride resin marking film to be adhered to stainless steel.