JP3283124B2 - Marking film containing fluorine resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine resin-containing marking film, and more particularly to a road exterior material, a building exterior material,
Fluorine resin-containing marking film with excellent adhesiveness and durability, used as a marking material for building materials such as roofing materials, parking lots, signboards, shutters, and wind signs, or as a transport material for automobiles, trains, ships, and aircraft. It is about.

[0002]

2. Description of the Related Art In general, designs such as patterns and colors are often applied to building materials and transportation equipment, and as a means for this, a method of manually applying a paint diluted with a solvent or the like has been adopted. I have. Therefore, work is easily affected by the weather,
In addition, there is a problem in that a bad odor is generated due to the scattering of the solvent, which is not preferable from the viewpoint of workability and worker safety and hygiene.

[0003] As means for solving such problems, conventionally, a marking film in which a strong adhesive is applied to a vinyl chloride resin film, a marking film in which an adhesive is applied to a polyester resin film, and an adhesive which is applied to a vinyl fluoride resin film. Marking film coated with agent
Various methods have been proposed for use as a marking material instead of the above paint.

According to such a marking film,
By sticking it to building materials and transport equipment, designs can be easily applied, and it has come to be used in a wide range of fields depending on the resin properties of films.

[0005]

However, the above marking film according to the prior art has a market demand in the field where long-term durability such as weather resistance is required. Was insufficient.

For example, in a marking film made of a vinyl chloride resin, the vinyl chloride resin and a plasticizer are used as main components for forming an adhesive film. There was a problem that it was inferior. Further, there is a problem that a marking film made of a polyester resin is inferior in water resistance and cannot withstand long-term use. Furthermore, although a marking film made of a vinyl fluoride resin has excellent durability, on the other hand, there is a problem that there is a selectivity of an adhesive due to a non-adhesive property peculiar to the fluororesin, and that adhesion to an adherend is poor. .

SUMMARY OF THE INVENTION An object of the present invention is to advantageously solve the problems of conventional marking films, such as inferior long-term durability and poor adhesion to adherends, and in particular, to improve the non-adhesion characteristic of fluororesins. Another object of the present invention is to provide a fluororesin-containing marking film having long-term durability.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies for realizing the above-mentioned object, and as a result, have conceived the present invention, which has the following constitution as a summary. That is, the present invention, 0.1 parts by weight of the vinylidene fluoride-containing resin,
Fluorine resin-containing film with the addition of amorphous SiO ₂ of 20 parts by weight, at least its one surface, a fluorine resin-containing marking film having excellent adhesion and durability formed by applying an adhesive. Further, the present invention provides, as the vinylidene fluoride-containing resin, an upper layer containing 80 to 50 parts by weight of a vinylidene fluoride resin and 20 to 50 parts by weight of a methacrylate resin, and 20 to 50 parts by weight of a vinylidene fluoride resin. A resin consisting of a lower layer containing 80 to 50 parts by weight of an acrylate resin is used.

[0009]

The feature of the present invention is that, by using a resin film of a mixture in which a predetermined amount of amorphous SiO ₂ is added to a fluororesin-containing film, permeation and permeation of oxygen and moisture into the resin film are achieved. And thereby improving the adhesion to the adherend. Thus, when amorphous SiO ₂ is added to the fluororesin, the amorphous SiO ₂ becomes
Suppress crystallization of fluororesin in resin film,
It acts to form a microscopically uniform composition and suppresses the permeation and penetration of oxygen and moisture into the film.

In the present invention, the amount of the amorphous SiO ₂ added to the fluororesin is determined based on the amount of the vinylilin-containing resin.
The amount of the outer frame is in the range of 0.1 to 20 parts by weight with respect to parts by weight.
The reason for this is that if the amount of amorphous SiO ₂ added is less than 0.1 part by weight, the effect of addition is small and the permeation of oxygen and moisture cannot be suppressed, and the adhesion to the adherend decreases. On the other hand, if the addition amount of amorphous SiO ₂ exceeds 20 parts by weight, the permeation amount of oxygen and moisture increases more than necessary, and discoloration and chalking of the film occur in a short time in the accelerated weathering test. Further, because the workability of the film is reduced, when the film is bonded to the adherend and processed, the film in the processed portion is cracked and the corrosion resistance is deteriorated.

The shape of the amorphous SiO ₂ is more effective as the particle size is smaller. If the particle size is more than 50 nm, the effect is not sufficiently exhibited, and rather, oxygen and moisture permeate more than necessary. As a result, the adhesion to the adherend decreases.

In the present invention, the reason for focusing on vinylidene fluoride-containing resin as the resin for the fluororesin-containing film is that it is the resin that is most easily formed of a film among the fluororesins, and the purchase price of these resins is low and economical. This is because it is also advantageous.

When the fluororesin-containing film made of the vinylidene fluoride-containing resin is a single layer, the methacrylate resin and the vinylidene fluoride resin are each preferably about 50 parts by weight from the viewpoint of film adhesion. desirable.
Of course, there is no practical problem with such a single-layer film, but the weather resistance is the lower limit of the fluorine film, and the addition amount of the methacrylate resin is as small as 50 parts by weight, so that the film adhesion is also the lower limit. Becomes For this reason, in order to share the functions, it is more preferable to form a film layer having a two-layer structure as described below. That is, in the film having the two-layer structure, the upper layer is a layer of a mixture of 80 to 50 parts by weight of vinylidene fluoride resin and 20 to 50 parts by weight of methacrylate resin, and the lower layer is 20 to 50 parts by weight of vinylidene fluoride resin. It is preferable to form a layer of a mixture of parts by weight and 80 to 50 parts by weight of a methacrylate resin.

In the case of such a film having a two-layer structure, when the content of the vinylidene fluoride resin in the upper layer film exceeds 80 parts by weight, it is advantageous for improving the weather resistance of the marking film. However, the processability of the film is reduced and the production cost is increased. On the other hand, when the content of the vinylidene fluoride resin is less than 50 parts by weight, the weather resistance of the resin itself is reduced, and therefore, a marking film having excellent long-term durability cannot be obtained.

On the other hand, when the content of the vinylidene fluoride resin in the lower film is less than 20 parts by weight, the adhesion to the adherend is improved, but the correlation adhesion to the upper film is reduced. When the content of the vinylidene fluoride resin exceeds 50 parts by weight, the adhesion to the adherend is reduced.

In the present invention, the pressure-sensitive adhesive applied to at least one surface of the above-mentioned fluororesin-containing film (in the case of a two-layer film, the side to which the lower film is adhered) is generally used for bonding the film. Any oil-based or water-based material may be used. For example, thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polyester, polyvinylidene chloride, nylon, polyvinyl alcohol, polystyrene, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, acrylic resin, polyoxymethylene, and epoxy resin Urea resin, melamine resin, thermosetting resin such as phenol resin, natural rubber, butyl rubber, isoprene rubber, butadiene rubber, thiocol, chloroprene rubber, nitrile rubber, styrene /
A single rubber or a mixture of two or more rubbers such as a butadiene copolymer is used. Above all, acrylic resin is advantageous in terms of adhesive strength to a fluorine-based resin.

In applying the pressure-sensitive adhesive to the fluororesin-containing film, any conventionally known method such as a knife coater method or a gravure roll coater coating method may be used. The reverse roll coater method, which is easy to adjust, can be advantageously applied since the type of the coating liquid is not selected.

In the present invention, the resin film may be colored and used. As such a coloring pigment, an inorganic pigment is preferably used from the viewpoint of weather resistance.
As the inorganic pigment, TiO ₂ which is generally commercially available
・ Sb ₂ OaO ・ NiO ・ Cr ₂ O ₃ as main component, titanium yellow type, ZnO ・ Fe ₂ O ₃・ Cr ₂ O ₃ component, zinc-iron type brown type, CoO ・ Al ₂ O ₃・ Cr ₂ Cobalt blue based on O ₃ , green based on TiO ₂ · CoO · NiO · ZnO, based on CuO · Cr ₂ O ₃ and CuO · Fe ₂ O ₃ · Mn ₂ O ₃ Various inorganic pigments such as a black pigment can be used. The amount of the coloring pigment to be added varies depending on the color tone, but is generally preferably 5 to 30 parts by weight based on 100 parts by weight of the resin component.

The above-described fluororesin-containing marking film of the present invention as described above can be suitably used for adherends such as plated steel sheets, painted steel sheets, and laminate-coated steel sheets. Above all, vinylidene fluoride resin
A two-layer film composed of an upper layer composed of 80 parts by weight and 20 parts by weight of a methacrylate resin and a lower layer composed of 20 parts by weight of a vinylidene fluoride resin and a methacrylate ester resin 80, to fluoride-containing resin 100 parts by weight, is particularly suitable when used for the fluorine resin-containing film-laminated steel sheet coated with a resin film obtained by adding the amorphous SiO ₂ 0.1 to 20 wt parts in the outer frame amount .

When the marking film according to the present invention is adhered to an adherend such as the above steel sheet, the marking film is thermally bonded to the previously heated steel sheet using a roll, or the marking film is directly attached to the steel sheet at room temperature. Any conventionally known method such as a method of manually sticking can be used. Therefore, such a bonding process is performed at a temperature of 100 ° C.
It is preferable to carry out by pressurizing for 5 to 3 minutes.

[0021]

【Example】

(Examples 1 to 12) (1) Preparation of adherend A fluororesin-containing film-laminated steel sheet was obtained by laminating a fluororesin-containing film on the surface of a 1.2-mm-thick hot-dip galvanized steel sheet that had been treated with zinc phosphate. . (2) Adhesion of marking film Using the fluororesin-containing film-laminated steel sheet obtained in the above (1) as an adherend, release the various types of marking films shown in Table 1 from the marking film and release the paper.
Roll-press bonding was performed at ℃ to prepare a resin film laminated steel sheet to which a fluororesin-containing marking film was adhered. The performance test of the resin film laminated steel sheet to which the various fluororesin-containing marking films thus obtained were adhered was performed according to the performance test items and test methods described later. Table 2 shows the test results.

(Comparative Examples 1 to 4) A resin having a fluororesin-containing marking film adhered thereto using the same fluororesin-containing marking film as the specifications shown in Examples 9 to 12 except that no amorphous SiO ₂ was added. A film laminated steel sheet was produced. Table 2 shows the performance test results of the resin film laminated steel sheet to which the fluororesin-containing marking film thus obtained was attached.

(Examples 13 to 15) A resin film laminated steel sheet having a fluororesin-containing marking film adhered thereto using the same fluororesin-containing marking film as the specification shown in Example 1 except that the kind of the adhesive is changed. Was prepared.
Table 2 shows the performance test results of the resin film laminated steel sheet to which the fluororesin-containing marking film thus obtained was attached.

As is evident from the results shown in Table 2, the resin film-laminated steel sheet to which the fluororesin-containing marking film of the present invention has been adhered can be obtained by applying the conventional marking film without addition of amorphous SiO _2. In comparison, corrosion resistance,
It was found that not only the weather resistance was excellent but also the film adhesion after the accelerated weather resistance test was remarkably excellent. If the resin film composition of the upper layer and the lower layer is within an appropriate range according to the present invention, a resin film-laminated steel sheet to which a fluororesin-containing marking film having excellent coating properties is adhered can be produced. Furthermore, even if the kind of the adhesive used for the fluororesin-containing marking film of the present invention was changed, the performance of the resin film laminated steel sheet to which such a marking film was adhered was excellent in adhesion and long-term durability. In addition,
In this example, an example was described in which a fluorocarbon resin-containing film-laminated steel sheet was used as an adherend, but similar results could be obtained even when another material was used as the adherend.

Performance Test Items and Test Methods [Coating Adhesion Test] Initial Adhesion Immediately after the marking film was adhered, the 180 ° C. peel adhesion was measured. The evaluation of the adhesive strength was as follows: ○: extremely excellent,
Δ: good, ×: fairly poor. -Normal adhesive strength The 180 ° C peel adhesive strength after standing at room temperature for 72 hours was measured. The determination of the adhesive strength was the same as the initial adhesive strength. [Weather Resistance Test] The test piece was put into a sunshine weather tester, and a weather resistance test was performed for 5,000 hours. In the evaluation of this test, the color difference and gloss remaining ratio in the plane portion of the film were measured, and the adhesion of the film was investigated. Judgment: Color difference (ΔE) → The smaller the value, the better the weather resistance. The gloss retention rate →% of the initial glossiness The better the value, the better the weather resistance. The adhesive strength → Same as the above initial adhesive strength [Corrosion resistance test] JIS It was evaluated according to Z2371 (salt spray test). The evaluation was evaluated as follows: ：: very good, Δ: good, ×: fairly poor. [Hot water-cooling shock test] 50 ° C hot water x 1 hour →-
20 cycles of 20 ° C. × 2 hours → room temperature × 1 hour → 50 ° C. hot water × 1 hour → −20 ° C. × 2 hours → room temperature × 17 hours. The determination of the adhesive strength was the same as the initial adhesive strength.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

As described above, in the marking film according to the present invention, since amorphous SiO ₂ is added to the resin film, the transmission of oxygen and moisture to the resin film is prevented.
Provides a fluororesin-containing marking film that not only excels in the effect of suppressing permeation, and in addition to excelling in corrosion resistance and weather resistance, but also has excellent film adhesion after accelerated weather resistance testing, as well as excellent adhesion and long-term durability. can do.
As a result, compared with the conventional vinyl chloride film and polyester-based marking film, the stain resistance is remarkably improved, and the cityscape can be maintained without losing the aesthetic appearance forever.

Continuation of front page (56) References JP-A-4-73824 (JP, A) JP-A-4-62132 (JP, A) JP-A-7-90152 (JP, A) JP-A-5-305694 (JP) JP-A-5-50566 (JP, A) JP-A-4-35938 (JP, A) JP-A-2-90637 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C09J 7/00-7/04 C08L 27/00-27/24 C08K 3/36

Claims (2)

(57) [Claims] An adhesive is applied to at least one surface of a fluororesin-containing film obtained by adding 0.1 to 20 parts by weight of amorphous SiO ₂ to 100 parts by weight of a vinylidene fluoride-containing resin. Marking film containing fluorine resin. 2. An upper layer containing the vinylidene fluoride-containing resin in an amount of 80 to 50 parts by weight of a vinylidene fluoride resin and 20 to 50 parts by weight of a methacrylate ester resin. The fluororesin-containing marking film according to claim 1, wherein the two layers are a lower layer containing 80 to 50 parts by weight of an acrylate resin.