JPH07188624A - Production of decorative pressure-sensitive adhesive sheet - Google Patents

Abstract

PURPOSE:To obtain a decorative pressure-sensitive adhesive sheet coated with a fluororesin, which scarcely suffers delamination and a decrease in weatherability, such as discoloration or fading. CONSTITUTION:A solution containing a fluororesin is applied on a release sheet and dried, and a vinyl chloride resin organosol is cast thefeon and cured by heating to form a laminated film consisting of a fluororesin film and a flexible vinyl chloride resin film. A pressure-sensitive adhesive layer is then laminated on the flexible vinyl chloride resin film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative pressure-sensitive adhesive sheet used for outdoor or indoor decoration or marking.

[0002]

2. Description of the Related Art Conventionally, there is known a decorative pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is laminated on one surface of an opaque, transparent or translucent mainly colored soft vinyl chloride resin film which is colored or patterned. This decorative pressure-sensitive adhesive sheet is applied to a material to be decorated by using an adhesive layer and exerts a decorative effect by coloring or patterning the surface side of the sheet. Instead of painting, a label or a sticker is used. It is used in the field of displays, such as advertisements and billboards, and in the field of fleet marking such as vehicle decoration (JP-A-63-54483, JP-A-2-84476, etc.).

The above-mentioned pressure-sensitive adhesive sheet for decoration has problems that it fades when it is exposed to the outdoors for a long period of time, and stains adhere to it due to wind and rain, exhaust gas, etc. and cannot be easily removed. Therefore, the surface of the colored soft vinyl chloride resin film has been coated with a fluororesin. The method for producing a fluorine-based resin-coated decorative adhesive sheet,
On the surface of the colored soft vinyl chloride resin film, for example, a solution of a mixture of a fluorinated terpolymer and an acrylic resin in an organic solvent, or a copolymer of a fluoroolefin and another vinyl group-containing monomer It was a method of directly applying an organic solvent solution or the like and drying.

[0004]

The pressure-sensitive adhesive sheet for decoration obtained by the above-mentioned manufacturing method is such that the soft vinyl chloride resin film is affected by the organic solvent in which the fluororesin is dissolved, and accelerated exposure and long-term outdoor use When exposed, there is a problem that deterioration progresses between the layers of the fluororesin layer and the soft vinyl chloride resin film, and eventually the fluororesin layer is peeled off, or discoloration or fading occurs and the weather resistance decreases. It was

The present invention is intended to solve the above problems, and the object thereof is to prevent peeling between the fluororesin layer and the soft vinyl chloride resin film layer even after long-term outdoor exposure, resulting in discoloration or fading. In other words, it is to provide a method for producing a fluorine-based resin-coated decorative pressure-sensitive adhesive sheet, which does not easily deteriorate in weather resistance.

[0006]

The method for producing a pressure-sensitive adhesive sheet for decoration according to the present invention comprises applying a fluororesin-containing solution onto a release sheet, drying the solution, casting a vinyl chloride resin organosol thereon, and then heat-curing the solution. Then, a laminated film of the fluororesin film and the soft vinyl chloride resin film is formed, and then an adhesive layer is laminated on the soft vinyl chloride resin film.

The fluorine-based resin used in the present invention is a polymer or copolymer of a fluorine-containing unsaturated monomer and a copolymer of a fluorine-containing unsaturated monomer and another monomer. Any solvent can be used as long as it can be dissolved in a solvent. Examples of the fluorine-containing unsaturated monomer copolymer include a fluorine-based terpolymer and a fluorine-based binary copolymer. For example, as the fluorine-based terpolymer, CH ₂ A terpolymer of CF ₂ , C ₂ F ₄ and C ₃ F ₆ is CH ₂ CF ₂ as a fluorine-based binary copolymer.
And C ₂ F ₄ binary copolymers. In the copolymer of the above-mentioned fluorine-containing unsaturated monomer and other monomer,
Examples of the other monomer include other monomers having a vinyl group. Examples of the copolymer of the fluorine-containing unsaturated monomer and the other monomer include a copolymer of C ₂ F ₄ and vinyl ether.

The fluororesin-containing solution used in the present invention includes, in addition to the above-mentioned fluororesin solution, a mixed solution of the above-mentioned fluororesin and an acrylic resin. The fluorine-based resin used in the above mixture is preferably a fluorine-based terpolymer or a fluorine-based binary copolymer. The acrylic resin refers to a homopolymer or copolymer of (meth) acrylic acid ester, or a copolymer of (meth) acrylic acid ester and another vinyl group-containing monomer, For example, polymethylmethacrylate, a copolymer of methylmethacrylate, a copolymer of 2-ethylhexyl acrylate, acrylic acid and vinyl acetate, etc. may be mentioned. In this case, the mixing ratio of the fluorinated resin and the acrylic resin is such that when the amount of the acrylic resin is small, the flexibility of the obtained film is poor, and when it is too large, the weather resistance is adversely affected. The amount of the resin is preferably 30 to 70 parts by weight.

An ultraviolet absorber may be further added to the fluororesin-containing solution used in the present invention in order to improve the weather resistance of the fluororesin film obtained by coating and drying this solution. As the ultraviolet absorber, a conventionally known ultraviolet absorber is used, and for example, a benzophenone-based or benzotriazole-based organic ultraviolet absorber, or ultraviolet rays such as ultrafine zinc oxide or titanium oxide that emit heat or long-wavelength ultraviolet light. Inorganic ultraviolet absorbers that convert to light are included. When the amount of the organic ultraviolet absorber used is small, the effect of absorbing ultraviolet becomes low, and when the amount is large, the ultraviolet absorber bleeds to the surface, so 0.1 to 2 parts by weight relative to 100 parts by weight of the fluororesin. Is preferred, and more preferably 0.1 to 1 part by weight.

In the present invention, the thickness of the fluororesin film obtained by coating and drying the above fluororesin-containing solution is preferably 10 to 30 μm. When the thickness is thin, the weather resistance is reduced, and when it is thick, the decorative effects such as the color and pattern of the vinyl chloride resin film are impaired, and the cutability when the decorative pressure-sensitive adhesive sheet is cut with a cutting machine and used is deteriorated.

The vinyl chloride resin organosol used in the present invention comprises a vinyl chloride resin, a plasticizer, and an organic solvent that does not substantially dissolve the resin, and is an organic solvent that does not substantially dissolve the vinyl chloride resin. Examples thereof include toluene, xylene, cellosolve, and methyl isobutyl ketone having a boiling point of 110 to 180 ° C.

The above-mentioned plasticizer is added as a component for softening the resin, and it is preferable to add about 25 to 60 parts by weight to 100 parts by weight of the resin. As the above-mentioned plasticizer, an adipic acid-based polyester plasticizer which is less likely to evaporate or migrate even when used outdoors for a long time is preferable.

Further, if necessary, the vinyl chloride resin organosol may be mixed with a pigment, a stabilizer, an ultraviolet absorber and the like.

The thickness of the soft vinyl chloride resin film produced from this vinyl chloride resin organosol is preferably 50 to 200 μm from the viewpoint of ease of use.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer used in the present invention needs to have a pressure-sensitive adhesive strength such that it cannot be peeled off after the decorative pressure-sensitive adhesive sheet is attached to an adherend. Examples thereof include urethane-based and silicone-based pressure-sensitive adhesives, but those based on acrylic resin are preferable from the viewpoint of adhesive strength, durability and the like. The thickness of this pressure-sensitive adhesive layer is 20 to 50 in terms of adhesion to an adherend and ease of use.
μm is preferred.

In the decorative pressure-sensitive adhesive sheet obtained by the production method of the present invention, the pressure-sensitive adhesive layer is preferably protected by a release sheet until use. The release sheet has a supporting force,
In addition, those having a release layer capable of releasing the pressure-sensitive adhesive layer on the surface, for example, various sheet materials such as paper, plastic, non-woven fabric, synthetic fiber, and a laminate of plastic and paper, silicone resin The thing coated with is mentioned.

The method for producing a decorative pressure-sensitive adhesive sheet of the present invention comprises:
First, a release sheet is used as a process paper, a fluororesin-containing solution is applied onto the release sheet and dried to form a fluororesin film, and then a vinyl chloride resin organosol is cast on the release sheet and heated to about 200 ° C. By doing so, a laminated film of a fluororesin film and a soft vinyl chloride resin film is formed, and then an adhesive layer is laminated on the soft vinyl chloride resin film.

Examples of the coating machine used for the above casting include a comma coater and a roll coater.

The release sheet used as the above-mentioned process paper is not particularly limited as long as it has a proper supporting force and can peel off the formed fluororesin film. Examples thereof include high-quality paper coated with alkyd resin and polyethylene terephthalate film coated with silicone resin.

In the step of laminating the pressure-sensitive adhesive layer on the soft vinyl chloride resin film, the compounding composition material of the pressure-sensitive adhesive is placed in a general-purpose or industrially used organic solvent such as toluene, xylene or ethyl acetate. A pressure-sensitive adhesive solution is obtained by dissolving and dispersing, and the pressure-sensitive adhesive solution is applied to the soft vinyl chloride resin film and dried to form a pressure-sensitive adhesive layer. The coating machine that can be used to form the pressure-sensitive adhesive layer is not particularly limited as long as it is used for ordinary pressure-sensitive adhesive solution coating, but preferably, the thickness can be accurately adjusted, Moreover, a knife coater, a comma coater, and a roll coater that can be applied with high productivity can be mentioned.

As a method for laminating the pressure-sensitive adhesive layer, the soft vinyl chloride resin film is directly coated with the pressure-sensitive adhesive solution and dried, or the release sheet is once coated with the pressure-sensitive adhesive solution and dried to form the pressure-sensitive adhesive layer. A transfer method in which the soft vinyl chloride resin film is laminated after being formed can be appropriately selected.

The decorative pressure-sensitive adhesive sheet produced in this manner is usually stored as a laminate in which a release sheet is attached to the pressure-sensitive adhesive layer surface as described above, and when used, the release sheet is removed from the pressure-sensitive adhesive layer surface. It is peeled off and used.

[0023]

According to the method for producing a pressure-sensitive adhesive sheet for decoration of the present invention, a fluororesin-containing solution is applied onto a release sheet, dried, and a vinyl chloride resin organosol is cast on the release sheet, followed by heat curing to give a fluororesin. Since a laminated film of a resin film and a soft vinyl chloride resin film is formed, the organic solvent in the fluororesin-containing solution has already volatilized at the time of making the soft vinyl chloride resin film. Does not affect Therefore, according to the production method of the present invention, even after long-term outdoor exposure, peeling is unlikely to occur between the layers of the fluororesin layer and the soft vinyl chloride resin film, discoloration, fading, etc. A coated decorative pressure-sensitive adhesive sheet is obtained.

Examples of the present invention will be described below.

【Example】

 Example 1 On a release sheet (process paper) for casting molding,
Fluorine resin coating [CH ₂CF₂, C₂F_FourAnd C₃F
₆Acrylic resin based on 100 parts by weight of the terpolymer
(2-ethylhexyl acrylate, acrylic acid and acetic acid
A vinyl copolymer) mixed at a ratio of 50 parts by weight.
Compound is methyl isobutyl ketone / methyl ethyl ketone
/ Dissolved in acetone composite solvent. Mizutani Paint
Co., Ltd.] to a thickness of 20 μm after drying, and then dry
Let it dry.

On top of this, a vinyl chloride resin organosol [vinyl chloride resin (Kanefuchi Chemical Co., trade name: PSH-1
0) 100 parts by weight, polyester plasticizer (manufactured by ADEKA ARGUS CORPORATION, trade name: P-300) 35 parts by weight, metal stabilizer (manufactured by ADEKA ARGUS CORPORATION, trade name: MARK-AP5)
51) 11 parts by weight, titanium oxide pigment (manufactured by Dainichiseika Co., Ltd., trade name: VT-771) 35 parts by weight, and solvent (Mitsubishi Petrochemical Co., Ltd., trade name: Solvesso) 60 parts by weight]
Is applied by casting and cured at about 200 ° C. to give a soft vinyl chloride resin film 50.
A laminated film having a thickness of 70 μm and a thickness of 70 μm was obtained.

Then, on the surface of the soft vinyl chloride resin film, 100 parts by weight of an acrylic pressure-sensitive adhesive [acrylic pressure-sensitive adhesive (P-44, manufactured by Soken Chemical Co., Ltd.) and an isocyanate-based curing agent (Coronate L-, manufactured by Nippon Polyurethane Co., Ltd.) were used. 55) 2 parts by weight] was applied so that the film thickness after drying would be 30 μm, and dried to produce the decorative pressure-sensitive adhesive sheet of the present invention. Next, release paper was laminated on the pressure-sensitive adhesive layer of the obtained decorative pressure-sensitive adhesive sheet and stored until use.

Example 2 A fluororesin paint (copolymer of C ₂ F ₄ and vinyl ether) dissolved in a methyl ethyl ketone / toluene / acetone composite solvent on a release sheet (process paper) for casting. Daikin Co., Ltd., trade name: Zeffle-LC) was applied so that the thickness after drying would be 30 μm.
Dried. On this, a vinyl chloride resin organosol was applied by casting in the same manner as in Example 1 and cured at about 200 ° C. to obtain a laminated film having a soft vinyl chloride resin film of 50 μm and a total thickness of 80 μm. Then, an acrylic pressure-sensitive adhesive was applied to the surface of the soft vinyl chloride resin film in the same manner as in Example 1 so that the film thickness after drying was 30 μm, and dried to prepare a decorative pressure-sensitive adhesive sheet of the present invention. Next, release paper was laminated on the pressure-sensitive adhesive layer of the obtained decorative pressure-sensitive adhesive sheet and stored until use.

Comparative Example 1 The vinyl chloride resin organosol of Example 1 was applied onto a release sheet (process paper) for casting molding to give about 20 parts.
A vinyl chloride resin film having a thickness of 50 μm was prepared by curing at 0 ° C., and the acrylic adhesive of Example 1 was dried on the vinyl chloride resin film to a thickness of 30.
It was applied so as to have a thickness of μm, dried, and release paper was laminated thereon to obtain a decorative pressure-sensitive adhesive sheet. The thickness of the decorative pressure-sensitive adhesive sheet after drying the fluororesin coating material of Example 1 was 20
By coating so as to have a thickness of μm and drying, a pressure-sensitive adhesive sheet coated with a fluororesin was obtained.

Comparative Example 2 The vinyl chloride resin organosol of Example 1 was applied onto a release sheet (process paper) for casting molding to give about 20 parts.
A vinyl chloride resin film having a thickness of 50 μm was prepared by curing at 0 ° C., and the acrylic adhesive of Example 1 was dried on the vinyl chloride resin film to a thickness of 30.
It was applied so as to have a thickness of μm, dried, and release paper was laminated thereon to obtain a decorative pressure-sensitive adhesive sheet. The thickness of the decorative pressure-sensitive adhesive sheet after drying the fluororesin coating material of Example 2 was 20
By coating so as to have a thickness of μm and drying, a pressure-sensitive adhesive sheet coated with a fluororesin was obtained.

(Performance Evaluation) The decorative pressure-sensitive adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to a weather resistance test as follows, and the results are shown in Table 1. Weather resistance test method The decorative pressure-sensitive adhesive sheet was subjected to accelerated exposure for 144 hours (corresponding to 3 years of outdoor exposure. The same applies hereinafter), 216 hours (corresponding to 5 years) with a Super UV tester (manufactured by Dainippon Plastics Co., Ltd.). 360 hours (equivalent to 8 years) and 432 hours (10
(Corresponding to a year) and the color difference with the decorative pressure-sensitive adhesive sheet not subjected to the weather resistance test was measured using a color difference meter (Σ-80 manufactured by Nippon Denshoku Co., Ltd.).

[0031]

[Table 1]

In Table 1, peeling means that peeling occurred between the layers of the fluororesin film and the soft vinyl chloride resin film.

[0033]

The structure of the method for producing a decorative pressure-sensitive adhesive sheet of the present invention is as described above, and a fluororesin-containing solution is applied onto a release sheet and dried, and a vinyl chloride resin organosol is cast thereon. Then, it is heat-cured to form a laminated film of a fluororesin film and a soft vinyl chloride resin film. Therefore, according to the production method of the present invention, the fluororesin layer and the soft vinyl chloride resin film are exposed even after long-term outdoor exposure. It is possible to obtain a fluorine-based resin-coated decorative pressure-sensitive adhesive sheet in which peeling between layers does not occur easily and weather resistance such as discoloration or fading does not easily deteriorate. Therefore, according to the production method of the present invention, a decorative pressure-sensitive adhesive sheet that can be suitably used outdoors can be obtained.

Claims (1)

[Claims] 1. A laminated film of a fluororesin film and a soft vinyl chloride resin film, which is obtained by applying a fluororesin-containing solution onto a release sheet, drying it, casting a vinyl chloride resin organosol on the release sheet, and then heat curing it. And a pressure-sensitive adhesive layer are laminated on the soft vinyl chloride resin film, and a method for manufacturing a pressure-sensitive adhesive sheet for decoration.