JPH073225A - Method for producing adhesive sheet having high chroma and used for decoration - Google Patents

Abstract

PURPOSE:To simply and efficiently obtain the subject sheet excellent in adhesivity, stain resistance and scratch resistance, and useful for labels, stickers, etc., by laminating an adhesive agent layer to the back surface of a white masking resin layer and subsequently laminating a colored transparent resin layer under specific conditions. CONSTITUTION:A method for producing the adhesive sheet comprises coating an organosol containing a white pigment on a processing paper sheet, heating the coated organosheet for forming a white masking resin layer, laminating an adhesive agent layer to the back surface of the white masking resin layer, peeling off the processing paper sheet, applying a low temperature cure type fluororesin or urethane resin solution containing a coloring pigment to the white masking resin layer of the processing paper sheet side, and subsequently drying the coated resin to laminate the colored transparent resin layer, or applying a low temperature cure fluororesin or urethane resin solution containing the coloring pigment to the back surface of the white masking resin layer, drying the coated resin solution for laminating the colored transparent resin layer, peeling off the processing paper sheet, and subsequently laminating the adhesive agent layer to the white masking layer surface on the side of the processing paper sheet.

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 having high saturation.

[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 resin sheet mainly made of polyvinyl chloride containing a pigment. This decorative pressure-sensitive adhesive sheet is affixed to a material to be decorated by using an adhesive layer, and exhibits a decorative effect by the color or pattern on the surface side of the resin sheet. In recent years, instead of painting, It is used in labels and stickers, displays such as advertisements and signs, and fleet markings such as vehicle decoration (for example, JP-A-63-54483 and JP-A-2-844).
No. 76).

Among these decorative pressure-sensitive adhesive sheets, in particular, for decorative pressure-sensitive adhesive sheets having high saturation, a colored transparent resin layer, a white concealing resin layer, and a pressure-sensitive adhesive layer, which have a lower pigment concentration to increase the saturation, are conventionally arranged in this order. The method for producing the organosol having a low pigment concentration is applied on a step paper to form a colored transparent resin layer by heating, and then an organosol containing a white pigment is formed on the colored transparent resin layer. By coating and heating, a white hiding resin layer is laminated, and further, an adhesive layer is laminated on the white hiding resin layer.

[0004]

In the above manufacturing method, since the organosol is used in the step of forming the colored transparent resin layer and the white hiding resin layer, the curing step at a high temperature of about 200 ° C. is required twice. Further, there is a problem that the solvent remains in the organosol and the adhesion between the two layers is deteriorated due to excessive curing. The present invention has been made in view of the above conventional problems, and an object thereof is about 20.
It is an object of the present invention to provide a method for producing a decorative pressure-sensitive adhesive sheet having a high saturation, which requires only one curing step at a high temperature of 0 ° C. and has good adhesion between two layers.

[0005]

The method for producing a high-saturation decorative pressure-sensitive adhesive sheet of the present invention comprises: (1) applying a white pigment-containing organosol onto a process paper and heating it to form a white hiding resin layer; (2) Next, after laminating an adhesive layer on the back surface of the white hiding resin layer, the process paper is peeled off, and a low temperature cure type fluorine resin or urethane resin containing a coloring pigment on the white hiding resin layer surface on the process paper side. A resin solution is applied and dried to laminate a colored transparent resin layer, or a low temperature cure type fluororesin or urethane resin solution containing a coloring pigment is applied and dried on the back surface of the white hiding resin layer to give a colored transparent resin. The layers are laminated, then the process paper is peeled off, and the pressure-sensitive adhesive layer is laminated on the white hiding resin layer side on the process paper side.

The organosol used in the present invention comprises a synthetic resin and an organic solvent which does not substantially dissolve the resin component, and the synthetic resin is not particularly limited as long as it can be a soft sheet. It is not something that is
Particularly preferred in the present invention is a vinyl chloride resin and an organic solvent which does not substantially dissolve the vinyl chloride resin, and an organic solvent of 30 to 150 relative to 100 parts by weight of the resin.
Organosols compounded in parts by weight can be mentioned. Furthermore, a white pigment for imparting a hiding property is added to the organosol in an amount of 10 to 100 with respect to 100 parts by weight of the resin.
It is preferable to add 25 to 60 parts by weight of a plasticizer as a component for softening the vinyl chloride resin and 100 parts by weight of the resin.

To coat the organosol on the process paper, for example, a casting method is used using a comma roll coater. The heating temperature after application is about 20.
About 0 ° C is preferable. The white hiding resin layer is formed in this manner, and the thickness of this layer is 30 to 20 in terms of ease of use.
0 μm is preferable.

As the low temperature cure type fluororesin solution containing the color pigment used in the present invention, a one-component type consisting of an organic solvent solution of the fluororesin and a fluororesin solution to which a curing agent is further added are used. There is a liquid type.
Examples of the one-liquid type include a vinylidene fluoride solution, and examples thereof include Florene (manufactured by Japan Synthetic Rubber Co., Ltd.), NEOFLON VT-100 (manufactured by Daikin Industries, Ltd.), Novacoat X.
PF-2105 (manufactured by Dainippon Color Materials Co., Ltd.) and the like can be mentioned.
Examples of the two-pack type include a fluoroolefin-vinyl ester copolymer (for example, Sepural coat, manufactured by Central Glass Co., Ltd.), a fluoroethylene-vinyl ether alternating copolymer (for example, Lumicro, manufactured by Asahi Glass Co., Ltd.) solution, and the like. In this case, the curing agent is preferably an isocyanate curing agent.

As the low temperature cure type urethane resin solution containing a color pigment used in the present invention, a one-pack type of an organic solvent solution of urethane resin and a urethane resin solution to which a curing agent is further added are used. There is a liquid type. As the one-liquid type, for example, Lamic FX-P
(Dainichi Seika Kogyo Co., Ltd.), FST (Toyo Ink Mfg. Co., Ltd.)
And so on. NB-300 as a 2-liquid type
(Manufactured by Dainichi Seika Kogyo Co., Ltd.), and an isocyanate curing agent is preferable as the curing agent.

The color pigment is preferably contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the resin so that a colored transparent resin layer can be obtained.

Examples of the method for applying the above resin solution on the white hiding resin layer include a coating method using a knife coater, a roll coater and the like and a screen printing method. The drying temperature after application is 40. ~ 100 ° C
A degree is preferable. The thickness of the colored transparent resin layer thus obtained is from 2 to 50 in terms of obtaining high saturation.
μm is preferred.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer used in the present invention includes, for example, rubber-based, urethane-based, silicon-based and acrylic-based pressure-sensitive adhesives. The base is preferred. The thickness of the pressure-sensitive adhesive layer is preferably 20 to 50 μm in terms of adhesive strength to an adherend and ease of use.

The method for laminating the pressure-sensitive adhesive layer on the white hiding resin layer is as follows. Dissolve the composition composition material of the pressure-sensitive adhesive in a general-purpose or industrially used organic solvent such as toluene, xylene or ethyl acetate. An adhesive solution by dispersing,
The adhesive solution is applied to the white hiding resin layer and dried to form an 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 the laminating method, in addition to the method of directly applying the adhesive solution to the white hiding resin layer and drying as described above, the adhesive solution is once applied to the release paper and dried to form the adhesive layer. After the formation, the transfer method by adhering to the white hiding resin layer can be appropriately selected.

The decorative pressure-sensitive adhesive sheet thus produced is usually stored as a laminate in which a release sheet is attached to the pressure-sensitive adhesive layer surface, and the release sheet is peeled off from the pressure-sensitive adhesive layer surface before use.

[0016]

According to the production method of the present invention, the colored transparent resin layer is produced by a method such as coating or printing of a low temperature cure type fluororesin or urethane resin without using the conventional organosol. Only one curing step at a high temperature of about 200 ° C is required.
Poor adhesion between the two layers due to residual solvent in the organosol and excessive cure, which are observed when organosol is used for both the colored transparent resin layer and the white hiding resin layer.
The problem is solved. Further, when a fluorine-based resin is used as the colored transparent resin layer, stain resistance can be imparted to the decorative pressure-sensitive adhesive sheet, and when a urethane-based resin is used, scratch resistance is imparted. Can be done.

[0017]

【Example】

(Example) FIG. 1 is an enlarged cross-sectional view of a decorative pressure-sensitive adhesive sheet obtained by the production method of the present invention, which comprises a colored transparent resin layer 1, a white hiding resin layer 2, a pressure-sensitive adhesive layer 3 and a release sheet 4. (1) First, in order to form the white hiding resin layer 2, the following vinyl chloride-based organosol composition was prepared with a dissolver stirrer, and this was processed with a comma roll coater (DNTP-NML, manufactured by Dai Nippon Printing Co., Ltd.). After coating and drying, 2
It was cured at 00 ° C. for 2 minutes to obtain a white hiding resin layer 2 having a thickness of 40 μm. "Organosol composition" Vinyl chloride resin (Zeon 121 manufactured by Zeon Corporation) 100 parts by weight Barium / zinc stabilizer (BZ-100J manufactured by Katsuta Kako Co., Ltd.) 2 parts by weight Benzotriazole ultraviolet absorber (manufactured by Ciba Geigy) Tinuvin 326) 0.5 parts by weight Polyester-based plasticizer (manufactured by ADEKA ARGUS CO., LTD., ADEKA SAIZER-PN446) 30 parts by weight Hydrocarbon-based solvent (manufactured by Shell Chemical Co., Solvesso # 150) 110 parts by weight White pigment (manufactured by Dainichiseika Co., Ltd.) , VT-SK-02) 60 parts by weight

(2) Next, 100 parts by weight of an acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive (P-44, manufactured by Soken Chemical Industry Co., Ltd.),
2% by weight of an isocyanate-based curing agent (Coronate L-55, manufactured by Nippon Polyurethane Industry Co., Ltd.) was mixed with release paper (Kite Chemical Co., SLK-110) 4 to obtain a film thickness after drying with a comma roll coater. After being coated so as to have a thickness of 30 μm and dried, the obtained pressure-sensitive adhesive layer 3 was attached onto the back surface of the white hiding resin layer 2 obtained in (1) above.

(3) Next, the process paper is peeled off, and on the surface of the white concealing resin layer 2 on the process paper side, a fluororesin solution containing a blue pigment (a vinylidene fluoride resin solution manufactured by Japan Synthetic Rubber Co., Ltd. ( Floren, nonvolatile content 46% by weight) 217 parts by weight,
A blue pigment (VT-SK-32, 8 parts by weight, manufactured by Dainichiseika Co., Ltd.) was applied by screen printing, and 60
Colored transparent resin layer 1 having a thickness of 30 μm after drying at 0 ° C. for 2 hours
To obtain a pressure-sensitive adhesive sheet for decoration. The obtained decorative pressure-sensitive adhesive sheet had high saturation.

Comparative Example In the step (3) of the example,
Instead of forming a colored transparent resin layer 1 having a thickness of 30 μm by applying a fluororesin solution containing a blue pigment by screen printing on the surface of the white concealing resin layer 2 on the process paper side and drying at 60 ° C. for 2 hours. Then, the following vinyl chloride-based organosol composition was coated on the surface of the white concealing resin layer 2 on the process paper side with a comma roll coater, dried and then cured at 200 ° C. for 2 minutes to form a colored transparent resin layer 1 having a thickness of 30 μm. A decorative pressure-sensitive adhesive sheet was obtained in the same manner as in the example except that it was formed. "Organosol composition" In the organosol composition used in the step (1) of the example, instead of adding 60 parts by weight of a white pigment (VT-SK-02, manufactured by Dainichiseika Co., Ltd.), a blue pigment (Dainichiseido Manufactured by Kasei Co., Ltd., VT-SK-32) 8
Same composition as used in step (1) of the example except that parts by weight were blended.

[0021] The following evaluations were conducted decorative pressure-sensitive adhesive sheet obtained in Comparative Example Evaluation Example as a sample. Adhesion test By using a cutter, a cross cut reaching the interface between the colored transparent resin layer and the white hiding resin layer was performed on the surface of the sample to make 12 20 × 20 mm goggles. After this sample was kept at 100 ° C. for 5 hours in a gar oven, the peeling condition between the layers was observed. As a result, no peeling occurred in the decorative pressure-sensitive adhesive sheet of the example, and it did not peel when peeled with a finger. In the case of the comparative example, peeling occurred from the end portion, and when peeled off with a finger, it was easily peeled off. Contamination resistance test A 200 × 200 mm sample was attached to an aluminum plate and exposed outdoors for 3 months. After the completion of the exposure, the surface of the sample was washed with water and the surface of the sample was observed. As a result, stains were easily washed off on the decorative pressure-sensitive adhesive sheets of Examples, but traces of stains remained on the decorative pressure-sensitive adhesive sheets of Comparative Examples.

[0022]

As described above, the method for producing a high-saturation decorative pressure-sensitive adhesive sheet of the present invention is as follows. Since the colored transparent resin layer is formed by using a low temperature cure type fluorine resin or urethane resin. Compared with the conventional method of producing a colored transparent resin layer and a white hiding resin layer with an organosol, the curing step at a high temperature of about 200 ° C. can be performed only once, so the production is simple and the colored transparent resin layer and white A decorative pressure-sensitive adhesive sheet having good adhesion between the two concealing resin layers can be obtained. Further, as the colored transparent resin layer, when using a fluorine-based resin, it is possible to impart stain resistance to the decorative pressure-sensitive adhesive sheet, and when using a urethane-based resin,
Scratch resistance can be imparted.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view of a decorative pressure-sensitive adhesive sheet obtained by the manufacturing method of the present invention.

[Explanation of symbols]

 1 Colored transparent resin layer 2 White hiding resin layer 3 Adhesive layer 4 Release sheet

Claims (1)

[Claims] 1. A white hiding resin layer is formed by applying (1) an organosol containing a white pigment onto a process paper and heating it. (2) Then, an adhesive layer is laminated on the back surface of the white hiding resin layer. After that, the process paper is peeled off, and a low temperature cure type fluororesin or urethane resin solution containing a coloring pigment is applied to the white concealing resin layer surface on the process paper side and dried to laminate a colored transparent resin layer, or White concealment resin layer A low temperature cure type fluororesin or urethane resin solution containing a coloring pigment is applied on the back surface and dried to laminate a colored transparent resin layer, then the process paper is peeled off and the white concealment on the process paper side is hidden. A method for producing a decorative pressure-sensitive adhesive sheet having high saturation, comprising laminating a pressure-sensitive adhesive layer on a resin layer surface.