JPH11241052A - Phosphorescent light-emitting adhesive tape and sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a phosphorescent light-emitting adheisve tape or sheet having a stable quality at a high mass-productivity by forming a phosphorescent light-emitting layer contg. a phosphoresent pigment and an epoxy resin on one side of a film substrate and forming a pressure-sensitive adhesive layer on the other side. SOLUTION: An adhesive tape having a protective layer formed on a phosphoresent light-emitting layer is provided, and a pressure-sensitive adhesive sheet having a release paper stuck to an adhesive layer is also provided. A phosphorescent coating soln. prepd. by dispersing a phosphorescent pigment in a liq. resin compsn. mainly comprising an uncured epoxy resin is applied to one side of a white film substrate 1 (e.g. a white polyester film) and thermally cured to form a phosphorescent light-emitting layer 2. On the phosphorescent light-emitting layer 2, a clear protective soln. such as of an acrylic resin is applied and heated to form an org. protective layer 3. On the other side of the white film substrate, an adhesive is applied and cured by heating or UV irradiation, thus forming an adhesive layer 4. A release paper 5 is stuck onto the adhesive layer 4 to give an adhesive sheet. Thus, a phosphorescent light-emitting adhesive tape or sheet which can be easily stuck to adherends of various materials with various shapes can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminous pressure-sensitive adhesive tape and sheet, and more particularly to a light-absorbing adhesive tape and sheet,
The present invention relates to a luminous pressure-sensitive adhesive tape and sheet that can luminesce and emit light in a dark place. Here, the tape means a band-like film-like object like a normal adhesive tape, and the sheet means a film-like object counted by the number of sheets like a normal document sheet.

[0002]

2. Description of the Related Art Conventionally, luminous pigments include clocks, wallpapers, adhesive tapes, signs and signs for disaster prevention and safety, fish hooks and other sporting goods, diver belts and other sporting goods, and the like.
It is widely used for clothing such as T-shirts and various accessories such as pendants.

The luminous pigments used in these various fields have the property of absorbing and accumulating light from the sun and fluorescent lamps themselves and emitting light in a dark place. Luminescent pigments are used in a wide range of applications because they have the property of being able to repeat absorption, luminescence and emission many times.

[0004] Luminescent pigments have a long history, and there have been many products that have been commercialized as phosphorescent adhesive tapes. However, if the afterglow time (time that can be discriminated by humans) is short and the afterglow time is long, Due to safety issues, including the inclusion of radioactive materials, it was not possible to obtain a large market.

However, in recent years, conventional phosphorescent pigments (for example,
Luminescent pigments containing strontium aluminate (SrAl ₂ O ₄ ) as a main component, whose afterglow time is at least one digit longer than that of ZnS: sulfides such as Cu (for example, JP-A-7-32418).
No. 6, JP-A-8-73845), since the phosphorescent adhesive tape has been developed in the fields of safety and disaster prevention, advertising and publicity, leisure goods and toys, etc. I'm taking a bath.

In the case of producing a phosphorescent adhesive tape, in order to obtain a product having excellent properties such as a long afterglow time, it is necessary to apply a thick ink containing a phosphorescent pigment on a support. In the case of a commonly used solvent-type luminous ink, the solvent contained during heating for drying and curing volatilizes, and when the coating is thick, air bubbles are likely to enter. The film thickness that can be processed was limited. For this reason, when producing a phosphorescent adhesive tape having excellent properties such as a long afterglow time, its mass productivity is poor and its improvement has been desired. Further, when the phosphorescent ink is applied thickly on the support, the support may be warped due to the curing shrinkage stress of the phosphorescent ink and the like, and improvement of the characteristics has been desired from such a viewpoint.

[0007]

As described above, it is difficult to stably produce a phosphorescent adhesive tape and sheet having excellent properties such as a long afterglow time with good mass productivity. Its development was strongly desired.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a phosphorescent adhesive tape and sheet having excellent properties such as a long afterglow time with good mass productivity and stability. In providing the quality we have.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to provide a strontium aluminate (SrA) which is excellent in phosphorescence and safety.
l ₂ O ₄ ) is coated on one side of a white base material such as a white polyester film with a luminous coating liquid in which a luminous pigment mainly composed of a non-solvent type epoxy resin is dispersed in a solvent-free epoxy resin. This can be achieved by producing a luminous adhesive tape and sheet, wherein a transparent organic paint is applied to form a protective layer, and an adhesive layer is provided on the other surface of the substrate.

The present inventors have conducted various studies on the materials constituting the luminous pressure-sensitive adhesive tape and sheet and the process for producing the same, and as a result, the dispersion medium of the luminous pigment in which the luminous pigment is dispersed is cationic polymerization. It has been found that a resin composition containing a non-solvent type epoxy resin as a main component may be used. Thereby, the phosphorescent light emitting layer can be coated with high productivity. Because the cationic polymerization is used for the curing reaction, there is no curing inhibition by oxygen, a dark reaction occurs, and the curing shrinkage is small. Thus, it has become possible to mass-produce luminous pressure-sensitive adhesive tapes and sheets having excellent properties and to manufacture products with stable performance.

[0011] Further, by using a luminous layer containing an epoxy resin as a dispersion medium, the adhesion to the substrate is improved, so that the durability of the luminous pressure-sensitive adhesive tape and sheet is improved, and the luminous layer is also improved. Since it was possible to impart flexibility to the luminescent adhesive tape and sheet, it was found that the curved surface had good adhesion to any adherend. Further, the luminous pressure-sensitive adhesive tapes and sheets of the present invention were superior to the luminous pressure-sensitive adhesive tapes and sheets using a polyvinyl chloride resin as a dispersion medium in light emission luminance and afterglow characteristics.

Hereinafter, the production of the luminous pressure-sensitive adhesive tape and sheet according to the present invention will be described with reference to FIG.

That is, first, a phosphorescent pigment is dispersed in a liquid resin composition containing an uncured epoxy resin as a main component on one surface of a film-like white substrate 1 made of white polyester or the like, both surfaces of which are anchor-coated in advance. The phosphorescent coating liquid thus formed is applied, and the resin composition is cured by heating to form the phosphorescent light-emitting layer 2. A transparent protective coating liquid such as an acrylic resin is applied thereon, and the organic protective layer 3 is formed by heating. Next, an adhesive is applied to another surface of the white base material 1, and an adhesive layer 4 is formed by heating, UV irradiation, or the like.
The phosphorescent adhesive tape according to claim 2 is obtained. In this manufacturing method, if the step of forming the organic protective layer 3 is omitted, the phosphorescent adhesive tape according to claim 1 is obtained.

Further, a release paper 5 is stuck on the pressure-sensitive adhesive layer 4 of the laminate comprising the white base material 1, the luminous light-emitting layer 2, the organic protective layer 3 and the pressure-sensitive adhesive layer 4. To obtain a phosphorescent adhesive sheet. In this manufacturing method, if the step of forming the organic protective layer 3 is omitted, the phosphorescent adhesive sheet according to claim 3 is obtained. The release paper 5 has a role of protecting the pressure-sensitive adhesive layer 4 of the photoluminescent adhesive sheet until immediately before use.

The phosphorescent pigment used here is MA
A compound represented by l ₂ O ₄ (where M represents at least one metal element selected from the group consisting of calcium, strontium, and barium) was used as a mother crystal, and europium was added as an activator to the mother crystal. An aluminate phosphorescent phosphor characterized by the above feature is used. But,
The phosphorescent phosphor is not limited to this composition.

Further, as the white base material, polyethylene,
A general-purpose organic polymer compound film such as polypropylene, polyester, ethylene-vinyl acetate copolymer, polystyrene, or polyvinyl acetate coated with a white paint, or a pre-whitened white polyester film or white polyethylene film it can. The film thickness may be in the range of tens to hundreds of μm.
A film having a thickness of 0 to 150 μm is preferable. The substrate is not limited to those described here as long as the film has a high light reflectance.

Next, as the resin composition of the phosphorescent coating liquid obtained by dispersing the phosphorescent pigment in the liquid resin composition, a solventless organic resin is desirable, and in particular, a cationic polymerizable epoxy resin as a main component is used. Things are desirable. As the epoxy resin, an epoxy compound obtained by glycidyl etherifying a hydroxyl group of bisphenol A, for example, an epoxy resin such as Epicoat 815, Epicoat 828, Epicoat 1001, Epicoat 1007 manufactured by Shell Chemical, or a compound having an alicyclic epoxy group, For example, Daicel Chemical Industries' Celloxide 2021, Celloxide 2081,
Alicyclic epoxy resin having two alicyclic epoxy groups such as celloxide 2083, M-1 manufactured by Daicel Chemical Industries, Ltd.
Alicyclic epoxy groups such as 00, A200, M101, etc.
Having acrylic or methacrylic monomers, or
Epoxidized polybutadiene resin, epoxidized polyester resin and the like can be used, and these are used alone or in the form of a mixture of two or more. In consideration of workability such as coating, it is desirable that the resin to be used is liquid at room temperature, either when used alone or as a mixture of two or more kinds.

It is to be noted that an organic resin such as an acrylic resin, a polyester resin, or a urethane resin may be added to the luminous coating solution using the solventless epoxy resin as a dispersion medium, if necessary. For curing the epoxy resin, an ordinary cationic polymerization catalyst that generates a Lewis acid by heating, an amine curing agent, and the like are used.

The proportion of the luminous pigment dispersed in the resin is adjusted according to the required afterglow time.
The phosphorescent pigment is used in an amount of 10 to 500 parts by weight based on 100 parts by weight of the resin. The desirable range is such that the luminous pigment is 50 to 300 parts by weight based on 100 parts by weight of the resin.

As a protective layer provided on the phosphorescent layer, an organic surface coating agent composed of an acrylic resin, a polyester resin, a urethane resin or the like can be used.
Thermosetting Sericol SP2100A manufactured by Teikoku Ink Manufacturing
U-clear or the like is used, but is not limited thereto. Usually, it is desirable that the film thickness is 10 to 100 μm.

As the material of the pressure-sensitive adhesive layer, an organic pressure-sensitive adhesive whose main component is an acrylic resin, silicone resin, natural rubber or synthetic rubber material is used. Examples of a method of applying the pressure-sensitive adhesive to a substrate include a method of directly applying and drying the film on a film, and a method of transferring a pressure-sensitive adhesive layer previously formed on another film to the substrate. The thickness of the pressure-sensitive adhesive layer is not particularly limited,
It is preferably in the range of several hundreds of μm, particularly 10 to 50 μm.
m is desirable.

The phosphorescent light-emitting adhesive tape is obtained by winding the phosphorescent light-emitting film thus produced into a roll, and a release paper is attached to the adhesive side of the film. obtain. In addition,
By cutting or punching as required, a luminous adhesive tape and sheet having a desired size and shape can be obtained.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the structures of the phosphorescent pressure-sensitive adhesive tape and sheet of the present invention will be specifically described with reference to embodiments. However, the present invention is not limited to these examples.

Embodiment 1 The present embodiment relates to a luminous pressure-sensitive adhesive tape according to claim 2 or a luminous pressure-sensitive adhesive sheet according to claim 4.

As a base material, a 75 μm-thick double-sided anchor-coated white polyester film was used, on which celloxide 2083 (manufactured by Daicel Chemical Industries) 8
100 parts by weight of an alicyclic epoxy resin composed of 0 parts by weight and 20 parts by weight of celloxide 2021 (manufactured by Daicel Chemical Industries, Ltd.) and CI-2624 as a cationic polymerization catalyst.
(Manufactured by Nippon Soda, solid content 50%), 10 parts by weight, SrAl
A luminous coating solution containing 100 parts by weight of a ₂ O ₄ : Eu-based luminous phosphor is applied and cured by heating at 120 ° C. for 30 minutes.
A phosphorescent layer having a thickness of about 300 μm was obtained. Subsequently, a surface coating agent (Sericol SP) manufactured by Teikoku Ink Manufacturing Co., Ltd.
-100 AU clear and curing agent in a weight ratio of 100: 1
4), and cured by heating at 60 ° C. for 2 hours to obtain a protective layer film having a thickness of 30 μm.

Subsequently, an acrylic pressure-sensitive adhesive (pressure-sensitive adhesive composition comprising 100 parts by weight of SLT-72-3 manufactured by Soken Chemical Co., Ltd. and 3 parts by weight of an isocyanate crosslinking agent) is applied to another surface of the white base material. Then, a pressure-sensitive adhesive layer having a thickness of about 30 μm was formed.
This is cut into a band, if necessary, and wound into a roll to obtain the phosphorescent light-emitting adhesive tape according to claim 2,
Further, a release paper was stuck on the pressure-sensitive adhesive layer, and was cut into a sheet as required, whereby a luminous light-emitting pressure-sensitive adhesive sheet according to claim 4 was obtained.

The phosphorescent adhesive tape and sheet were affixed to a stainless steel plate, an aluminum plate, a soft vinyl chloride resin, a hard vinyl chloride resin, an acrylic resin, an ABS resin and the like, and the adhesive properties were evaluated. Good characteristics were shown. Next, an outdoor exposure test was performed, and there was no discoloration even when left for one month or longer.
It exhibited excellent weather resistance. Further, a change in afterglow luminance after irradiating the phosphorescent adhesive tape and sheet with light of 15,000 lux for 10 minutes was measured. The afterglow luminance attenuated with the standing time, but sufficient light emission was observed even after standing for 2 hours or more, and it was confirmed that good afterglow characteristics were exhibited.

Embodiment 2 The present embodiment also relates to the luminous adhesive sheet or the luminous adhesive sheet according to claim 4.

As a base material, a white polyester film having a thickness of 100 μm and subjected to a double-sided anchor coating treatment was used.
On top of this, 100 parts by weight of an epoxy resin composed of celloxide 2083 (50 parts by weight) and Epicoat 828 (50 parts by weight, manufactured by Shell Chemical Co.) were added to CI-2624, a cationic polymerization catalyst (manufactured by Nippon Soda, solid content 50%). %) To 6
Parts by weight and 150 parts by weight of a SrAl ₂ O ₄ : Eu based phosphorescent phosphor.
The phosphorescent coating liquid added by weight was applied so as to have a thickness of about 200 μm, and was cured by heating at 120 ° C. for 10 minutes. Subsequently, a surface coating agent manufactured by Teikoku Ink Manufacturing Co. (mixture of Sericol SP-2100AU Clear and a curing agent at a weight ratio of 100: 14) was applied thereon, and cured by heating at 60 ° C. for 2 hours. Then, an organic protective layer having a thickness of 50 μm was obtained.

Subsequently, a pressure-sensitive adhesive composition comprising 100 parts by weight of an acrylic pressure-sensitive adhesive (SK Dyne 1604 manufactured by Soken Chemical Co., Ltd.) and 2 parts by weight of an isocyanate cross-linking agent was applied to the other surface of the white base material, to a thickness of about 30 μm. A thick adhesive layer was formed. This is cut into a band as necessary and wound into a roll to obtain the phosphorescent adhesive tape according to claim 2, and a release paper is adhered on the adhesive layer, if necessary. Then, the phosphorescent adhesive sheet according to claim 4 was obtained by cutting into a sheet shape.

The phosphorescent pressure-sensitive adhesive tape and sheet were affixed to a stainless steel plate, an aluminum plate, a soft vinyl chloride resin, a hard vinyl chloride resin, an acrylic resin, an ABS resin and the like, and the adhesive properties were evaluated. Good characteristics were shown. Next, an outdoor exposure test was performed, and there was no discoloration even when left for one month or longer.
It exhibited excellent weather resistance. Further, a change in afterglow luminance after irradiating the phosphorescent adhesive tape and sheet with light of 15,000 lux for 10 minutes was measured. Although the afterglow luminance attenuated with the standing time, the light emission was sufficiently observed even after the standing for one hour or more, and it was confirmed that the luminance was good.

Embodiments 3 to 10 In the same manner as in Embodiments 1 and 2, Tables 1 and 2 were prepared by using a SrAl ₂ O ₄ : Eu-based phosphorescent phosphor on a 75 μm thick white polyester film. The phosphorescent light-emitting pressure-sensitive adhesive sheet was prepared by providing the phosphorescent light-emitting layer under the conditions shown below. When various evaluation tests were performed, it was confirmed that all of the evaluation tests had sufficient afterglow characteristics and weather resistance.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

As described above, the problem of the prior art can be solved by forming the luminous adhesive tape and sheet into the tape and sheet of the present invention.
It is possible to provide a luminous adhesive tape and sheet having good productivity, excellent afterglow characteristics, weather resistance, etc., and which can be easily attached to adherends of various shapes and materials. As a result, the phosphorescent adhesive tapes and sheets having excellent performance can be used for a wide range of applications such as safety or disaster prevention, advertising and publicity, leisure goods and toys.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a procedure for producing a luminous pressure-sensitive adhesive tape and sheet of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... White base material, 2 ... Photoluminescent layer, 3 ... Protective layer, 4 ... Adhesive layer, 5 ... Release paper.

Claims (4)

[Claims] 1. A film-like substrate, a luminous layer containing a luminous pigment and an epoxy resin provided on one surface of the substrate, and an adhesive layer provided on the other surface of the substrate. A phosphorescent adhesive tape characterized by having: 2. A film-like base material, a luminescent layer containing a luminous pigment and an epoxy resin provided on one surface of the substrate, and an organic protective layer provided on the luminescent layer. And a pressure-sensitive adhesive layer provided on the other surface of the base material. 3. A film-like substrate, a luminous layer containing a luminous pigment and an epoxy resin provided on one surface of the substrate, and an adhesive layer provided on the other surface of the substrate. And a release paper attached to the pressure-sensitive adhesive layer. 4. A film-like base material, a luminescent layer containing a luminous pigment and an epoxy resin provided on one surface of the substrate, and an organic protective layer provided on the luminescent layer. A phosphorescent light-emitting pressure-sensitive adhesive sheet, comprising: a pressure-sensitive adhesive layer provided on the other surface of the substrate; and a release paper stuck on the pressure-sensitive adhesive layer.