JPH089221B2 - Fluorescent sheet and manufacturing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent sheet with high weather resistance, and uses the high visibility of fluorescent colors to make it safe for signboards, wind stickers, etc. in the fields of advertising, publicity and decoration.
The present invention relates to a fluorescent sheet used for marking, identifying a pipe in the field of disaster prevention.

[0002]

2. Description of the Related Art In recent years,
Various types of fluorescent sheets are produced, and most of them are processed with an adhesive or the like suitable for the purpose, and are widely used for signboards, stickers, etc. due to their high visibility of fluorescent colors and their ease of processing. Further, a fluorescent dye, which is a base of coloring property of a fluorescent sheet, has been developed, and a high-performance fluorescent pigment has been developed by dyeing the fluorescent dye into a fine powder.

However, most of the present fluorescent sheets use a solvent-based coating agent in which a fluorescent pigment, an ultraviolet absorber, etc. are kneaded in a solvent-based varnish for the fluorescent coloring layer and the ultraviolet absorbing layer,
The sheet strength or the like mainly depends on the white or co-colored vinyl chloride film or the like used for the reflective layer. As a result, in the case of a white or co-colored vinyl chloride film, it is necessary to have both the required hiding rate as a reflective layer and a large contribution to the sheet strength, and therefore, in the practical calendar method, 70 μm, Even in the sol coating method, a minimum film thickness of 50 μm was required. Further, in the case of a fluorescent sheet, the overall thickness is different depending on the application, but generally, the thinner the better, as long as the fluorescent color can be maintained without any problem in weather resistance. When a certain amount of thickness is required, it can be easily thickened by laminating it with another film, but when thinness is required, the fluorescent coloring layer is thinned at the expense of weather resistance. Was there.

Accordingly, an object of the present invention is to provide a thin type fluorescent sheet which has high saturation and weather resistance.

[0005]

According to the present invention, (A)
Visible light transmittance 70% or more, ultraviolet light transmittance 0-30
%, The ultraviolet absorbing layer made of a film having a film thickness of 5 to 150 μm, (B) a fluorescent coloring layer having a film thickness of 50 to 200 μm, and (C) a hiding ratio of 70% or more and a film thickness of 5 to 50 μm.
There is provided a fluorescent sheet provided with the reflective layer.

[0006] In the fluorescent coloring layer, the thicker the coating containing a large amount of the fluorescent pigment having good weather resistance is, the more the coloring property and the weather resistance are improved, but since the amount of the fluorescent pigment is large, the contribution to the sheet strength is small. . In addition, when the fluorescent coloring layer is dyed with a fluorescent dye or mixed with a fluorescent pigment in a transparent vinyl chloride resin to be colored and formed into a film by a thermal calendar method or a sol coating method, the sheet strength depends on the fluorescent coloring layer. Although it is possible to do so, the color developability, weather resistance and the like tend to deteriorate.

Therefore, in the present invention, the sheet strength is mainly dependent on the ultraviolet absorbing layer, and the reflecting layer, which has conventionally been dependent on the sheet strength and the like, contains a large amount of a coloring agent such as titanium white to conceal the hiding rate. It was possible to reduce the film thickness by using a coating layer of improved white paint. Furthermore, it has become possible to easily add an adhesive function, an adhesive function, a co-coloring function, etc. while maintaining the reflection function. Further, in the past, a fluorescent coloring layer was provided by coating on the reflective layer in the process, and an ultraviolet absorbing layer was further provided by coating, but in the present invention, basically, fluorescent coloring is provided on the ultraviolet absorbing layer. Since the layers are provided by coating and finally the reflecting layer is provided by coating, the lot number of the reflecting layers can be reduced, and the co-coloring function, the adhesive function, the adhesive function, etc. can be easily added.

First, the ultraviolet absorbing layer will be described. The UV absorbing layer, which is made by dissolving and dispersing UV absorbing agent in resin, has a tensile strength of 600 gf / 10 mm or more, a tensile elongation of 10% or more (test method: JIS Z0237 item 6, tensile strength and elongation) and sheet strength. This film has a large contribution and has a visible light (400 to 720 nm) transmittance of 70% or more and an ultraviolet ray (400 nm or less) transmittance of 0 to 30%.

As the ultraviolet absorber, an organic ultraviolet absorber such as benzotriazole-based tinuvin 32 is used.
8, Tinubin 900 (Ciba Geigy), Mark L
A-32 (manufactured by Asahi Denka Co., Ltd.); benzophenone-based Ubinal D-49 (manufactured by BASF), Siasolv UV-
24 (American Cyanamid), Mark 1413
(Manufactured by Asahi Denka Kogyo Co., Ltd.);
As an inorganic ultraviolet absorber such as SU (manufactured by Sando), for example, ultrafine zinc oxide ZnO-100 (manufactured by Sumitomo Cement); ultrafine titanium oxide IT-S (manufactured by Idemitsu Kosan) They can be used alone or in combination of two or more. An antioxidant or a light stabilizer may be used alone or in combination of two or more kinds with the above ultraviolet absorber. As an antioxidant,
For example, phenolic Irganox 1010 (Ciba
Geigy), Mark AO-20 (Asahi Denka Kogyo), phosphite-based mark PEP-36 (Asahi Denka Kogyo), and thioether-based mark AO-23 (Asahi Denka Kogyo). To be Examples of the light stabilizer include hindered amine type mark LA-57 (manufactured by Asahi Denka Kogyo Co., Ltd.), Sanol LS-744 (manufactured by Sankyo Co., Ltd.) and the like.

The ultraviolet absorbing layer is formed by dissolving or dispersing the above-mentioned ultraviolet absorbing agent in a solvent type resin such as an acrylic resin type, a vinyl chloride resin type, a urethane resin type, a cellulose resin type, a fluororesin type or an acrylic silicone resin type. Varnish; acrylic resin emulsion, ethylene-vinyl acetate resin emulsion, etc., water-based resin varnish such as vinylidene chloride resin latex, etc .; vinyl chloride resin paste, vinyl chloride-vinyl acetate copolymer resin paste, etc., either alone or 2
Combinations of two or more types are used to coat release paper, release film, etc. with a knife coater, reverse coater, comma doctor, etc. It can also be obtained by a calendar method or the like using a vinyl chloride resin compound. The mixing ratio of the ultraviolet absorber to the resin is 0.5 to 15 p. h. r, the dispersion type inorganic ultraviolet absorber has a weight ratio of 5 to 40 p. h.
r is desirable.

The ultraviolet absorbing layer may be composed of a composite layer of a transparent film that makes a large contribution to the sheet strength and a layer that makes a small contribution to the sheet strength but has an ultraviolet absorbing function. Examples of the transparent film that greatly contributes to the sheet strength include Lumirror (manufactured by Toray), Tetoron film (manufactured by Teijin), Dia foil (manufactured by Mitsubishi Diamond foil), Toyobo ester film (manufactured by Toyobo), and Emblet ( An ultrathin (3 to 10 μm) biaxially stretched polyester film that is strong in strength and heat, such as manufactured by Unitika. Since the polyester film has poor adhesion to the fluorescent coloring layer, a layer having an ultraviolet absorbing function often serves the purpose of improving the adhesion. In this case, the ultraviolet absorbing layer is formed by coating the polyester film with a coating material or ink containing an ultraviolet absorbing agent using a reverse roll coater, a gravure coater or the like.

Further, the transparent film has a gas barrier property,
In order to impart strength and the like, a multilayer film of various transparent films such as a polyolefin resin composite film can also be used.

Further, the ultraviolet absorbing layer may be composed of an ultraviolet absorbing film. As the ultraviolet absorbing film, acrylic acrylene (manufactured by Mitsubishi Rayon Co., Ltd.), Hi-S A film (manufactured by Nippon Carbide Industry Co., Ltd.), Sunduren (manufactured by Kanegafuchi Chemical Industry Co., Ltd.), etc .; acrylic vinyl acrylide (manufactured by Mitsubishi Rayon Co., Ltd.) Etc .; PVC-based Hi-S N film (manufactured by Nippon Carbide Industry Co., Ltd.); Fluorine-based Kureha KFC film (manufactured by Kureha Chemical Industry Co., Ltd.), DX film (manufactured by Denki Kagaku Kogyo Co., Ltd.), etc .; Polyester-based Tetron H
B (manufactured by Teijin Ltd.) and the like.

Next, the fluorescent coloring layer will be described. The fluorescent coloring layer needs to have a film thickness of 50 to 200 μm.

Examples of the fluorescent pigment include amino resin pigments dyed with a fluorescent dye, FZ2000 series (manufactured by Shin Loihi), FZ5000 series (manufactured by Shin Loihi), FZ3040 series (manufactured by Shin Loihi), FA.
Series (Shin Roihi), NKP-8300 Series (Nippon Fluorescent Chemicals), T Series (Day Glow)
Acrylic resin pigment SW series (manufactured by Shin Loihi Co.), SP series (manufactured by Shin Roihi Co., Ltd.), NKW-2100 series (manufactured by Nippon Fluorescent Chemical Co., Ltd.) and the like can be used. . These may be used alone or in combination of two or more as required.

As a general pigment which can be used in combination with the fluorescent pigment when more weather resistance is required, for example, as a yellow pigment, a monoazo type Hansa Yellow 10G (manufactured by Hoechst).
First Yellow 10G (manufactured by Sanyo Dye Co., Ltd.), Monolight First Yellow 10G (manufactured by ICI), Monoazo Permanent Orange RL01 (manufactured by Hoechst) as an orange pigment, Molybdate Orange P380 (manufactured by Dainichiseika Kogyo Co., Ltd.), Hansa Orange RN (made by Hoechst),
Anthraquinone type Cardon Gold Orange G (IC
Made by I.), Indanthrene Gold Orange G (BAS
Company F), monoazo-based Nova Palm Red HF4B (manufactured by Hoechst) as a red pigment, Permanent Red FN
G (manufactured by Sanyo Pigment Co., Ltd.), Mono Light Red 4RH (ICI
), As a green pigment, phthalocyanine-based heliogen green G (manufactured by BASF), lionol green 6Y
-501 (manufactured by Toyo Ink Mfg. Co., Ltd.) or the like can be used. These may be used alone or in combination of two or more as required. Further, for the purpose of improving weather resistance, the above-mentioned UV absorbers (organic and inorganic) are added, and further antioxidants (hindered amine-based, high-molecular weight phenol-based, etc.) having a great synergistic effect with the UV absorber are added. be able to.

The fluorescent colored layer is formed by an acrylic resin type, a vinyl chloride resin type, a urethane resin type, a cellulose resin type,
Fluorine resin-based, alkyd resin-based, acrylic silicone resin-based, polyamide resin-based and non-aqueous acrylic emulsion-based solvent-based resin varnishes; acrylic resin-based emulsions, ethylene-vinyl acetate resin-based emulsions, vinylidene chloride resin-based latex, etc. A water-based resin varnish is used alone or in combination of two or more kinds, and a fluorescent pigment or a resin in which a general pigment, an ultraviolet absorber, an antioxidant and the like are dispersed if necessary, a knife coater on the ultraviolet absorbing layer, It is performed by coating with a reverse coater, comma doctor, etc. In this case, the blending ratio of the fluorescent pigment to the resin is preferably 1/1 or more in terms of color development and weather resistance.

In any case, since the fluorescent coloring layer is provided on the ultraviolet absorbing layer by coating, the resin used is appropriately mixed with a resin depending on the material of the ultraviolet absorbing layer, the coating method, the drying method and the like. When the material of the ultraviolet absorbing layer is a vinyl chloride type, the fluorescent coloring layer can be provided by a vinyl chloride sol type. Further, when the ultraviolet absorbing layer is an acrylic film or a vinyl chloride film, heat lamination is possible. As a method of making good use of the workability of thermal lamination, there is a method of previously providing a fluorescent coloring layer. For example, release paper may be coated with a fluorescent paint to provide a fluorescent coloring layer, and heat laminated, or vinyl chloride resin may be colored with a fluorescent pigment or fluorescent dye and heat laminated by a calendar method.

Next, the reflective layer will be described. The reflection layer needs to have a hiding ratio of 70% or more. Since it is not necessary for the reflective layer to depend on the sheet strength, a large amount of titanium oxide pigment or the like can be contained in the reflective layer. Examples of titanium oxide pigments include rutile type TAIPAKE R-820 (manufactured by Ishihara Sangyo Co., Ltd.), titanium oxide R-650 (manufactured by Sakai Chemical Industry Co., Ltd.), KRONOS KR380N (manufactured by Titanium Industrial Co., Ltd.), TAIPAKE R.
-930 (manufactured by Ishihara Sangyo Co., Ltd.), Thai Pure R-900
(Manufactured by DuPont) and the like.

The same resin as the fluorescent colored layer can be used as the resin, and the resin is appropriately selected according to the material of the fluorescent colored layer and the coating method. Further, since it is easy to give a co-coloring function, an adhesive function, an adhesive function, etc., it is appropriately selected according to the application. For example, a white adhesive layer in which titanium oxide is dispersed in an adhesive resin can be used as the reflective layer.

In the case of fluorescent color as the reflective layer, white is usually used from the viewpoint of sharpness, and the higher the hiding ratio, the better. In the present invention, since it is not necessary to depend on the sheet strength, it is necessary to form a thin reflective layer by thinly coating a paint, an ink or the like containing a large amount of a titanium dioxide pigment having a high white hiding power. Became possible.

The basic structure of the present invention has been described above.
When priority is given to long-term weather resistance over clarity of the fluorescent color, a general color pigment or a soluble dye is added to the fluorescent coloring layer, or a general color pigment or a dissolution pigment is added to the reflective layer. It is also possible to add a type of dye-added paint or the like. As in the fluorescent pressure-sensitive adhesive sheet of Japanese Patent Application No. 2-209188, it is also possible to provide a transparent and weather-resistant co-color layer between the fluorescent colored layer and the reflective layer. The reflective layer may have an adhesive function or a co-coloring function depending on the purpose of use. It is also possible to use a plastic film, synthetic paper, paper, plywood, color tin or the like as the reflective layer by interposing an adhesive layer between the fluorescent coloring layer and the reflective layer.

Since the fluorescent pressure-sensitive adhesive sheet of the present invention has high weather resistance and a thin film thickness, it can be used for a long period of time in a wide range of fields such as signboards, wind sticker signs, vehicles, electric appliances and the like.

[0024]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Example 1] Acryprene HBS (acrylic ultraviolet absorbing film, manufactured by Mitsubishi Rayon Co., Ltd.) having a film thickness of 50 μm was used as a fluorescent red coating agent by weight: SW13 (fluorescent pigment, manufactured by Shin Loihi Co.) 28.00 FZ5013 ( Fluorescent pigment, manufactured by Shin Roihi Co., Ltd. 20.00 Sand bar 3041 (UV absorber, manufactured by Sand Co.) 0.20 Deformer 1512 (antifoaming agent, manufactured by Dick Hercules Co., Ltd.) 0.50 Polyzole AD-5 (ethylene vinegar vinyl emulsion) Binder, manufactured by Showa High Polymer Co., Ltd.) 47.00 Water 4.30 100.00 The red fluorescent paint consisting of the above was prepared at 25 ° C. and 8 poise, and coated with a knife coater to a film thickness of 180 μm.
It was dried for 5 minutes in a hot air drying oven kept at 0 ° C. to obtain a dry film thickness of 85 μm (total film thickness of 135 μm).

As a reflective layer thereon, parts by weight HEC (hydroxyethyl cellulose, manufactured by Hoechst) 0.30 water 33.40 TW-R-900 (TiO ₂ , manufactured by DuPont) 40.00 Dimol EP (surfactant) , Kao) 0.80 Deformer 1512 (Antifoam, Dick Hercules) 0.50 Polysol AD-5 (Ethylene vinegar emulsion binder, Showa High Polymer Co., Ltd.) 25.00 100.00 From above White paint is prepared at 25 ° C and 20 poise and coated with a reverse roll coater to a film thickness of 100 μm.
The white reflective layer having a dry film thickness of 30 μm (total film thickness of 165 μm) was obtained by drying for 4 minutes in a hot air drying oven kept at 00 ° C.

The red fluorescent sheet having a total film thickness of 165 μm obtained here has a tensile strength of 2080 g / cm width and an elongation of 40%.
And the sheet strength was excellent. Adhesive processing was performed on the white reflective layer side of this red fluorescent sheet with an emulsion type adhesive, AT-22 (manufactured by Saiden Chemical Co., Ltd.) to produce an adhesive fluorescent sheet, which was a commercially available product, Lumino Tape # 203, red and weather resistant. Excellent results were obtained by comparison.

Further, when weather resistance is required, it is possible to use a red paint of a general color which is excellent in weather resistance and is clear for the reflective layer.

Another feature of this system is that it is a water-based paint system, so it is eliminated from the risk of air pollution and explosion.

[Example 2] Fluorescent lemon yellow coating agent on Sunduren SD001 (acrylic UV absorbing film, manufactured by Kanebuchi Chemical Co., Ltd.) having a film thickness of 30 μm, as a part by weight, SP15 (fluorescent pigment, manufactured by Shin Loihi) 30 0.0000 FZ3045S (fluorescent pigment, manufactured by Shin Roihi) 20.00 Sand bar 3041 (ultraviolet absorber, manufactured by Sand Co.) 0.02 Deformer 1512 (antifoaming agent, manufactured by Dick Hercules) 0.50 Polyzole AD-5 ( Ethylene acetate vinyl emulsion binder, Showa High Polymer Co., Ltd.) 46.00 Water 3.48 100.00 A lemon yellow fluorescent coating material comprising the above was obtained in the same manner as in Example 1 to obtain a dry film thickness of 85 μm (total film thickness of 115 μm). .

On top of that, as a reflection layer, parts by weight HEC (hydroxyethyl cellulose, manufactured by Hoechst) 0.14 water 13.66 TW-R-900 (TiO ₂ , manufactured by DuPont) 40.00 EM color Yellow FX-2107 ( Toyo Ink Co., Ltd.) 20.00 Dimol EP (surfactant, manufactured by Kao Co.) 0.70 Deformer 1512 (antifoaming agent, manufactured by Dick Hercules Co., Ltd.) 0.50 Polyzole AD-5 (ethylene vinegar vinyl emulsion binder, Showa High Polymer Co., Ltd.) 25.00 100.00 The lemon yellow paint having the above-mentioned hiding power was processed in the same manner as in Example 1 to obtain a dried film thickness of lemon yellow of 3
A 2 μm reflective layer was obtained. (Total film thickness 147 μm).

The lemon yellow fluorescent sheet thus obtained was excellent in sheet strength with a tensile strength of 1420 g / cm width and an elongation of 32%.

An excellent result was obtained when the reflective layer of the co-colored lemon yellow of this fluorescent lemon yellow sheet was treated with an adhesive in the same manner as in Example 1 and the weather resistance was compared with the commercially available Lumino Tape # 205 Lemon Yellow. Was given.

[Example 3] 6 μm ultra-thin polyester film of Diamond foil # 6 (manufactured by Diamond Foil) as an ultraviolet absorbing layer by weight UE-3221 (polyester resin, manufactured by Unitika Ltd.) 20.00 Toluene (solvent) 60 0.000 Methyl ethyl ketone (solvent) 20.00 Tinuvin 900 (ultraviolet absorber, manufactured by Ciba Geigy) 1.50 101.50 resin solution was adjusted to 5 poise and the entire surface was coated with a gravure plate with a plate depth of 60 μm to give a dry film thickness. A coating of 10 μm is obtained.
As a result, the 6 μm diamond foil # 6 and the coating film 1 as the base material
0 μm total film thickness 16 μm, tensile strength 1300 gf
A film excellent in strength having a width of / 10 mm and an elongation of 120% was obtained.

Next, as a fluorescent paint, parts by weight Acrybase 703 (40% acrylic resin toluene solution manufactured by Fujikura Kasei Co., Ltd.) 50.00 Shinrehi Color FZ5013 (red fluorescent pigment, manufactured by Shinrehi Co., Ltd.) 40.00 Disparon 4200-20 ( Pigment dispersant, manufactured by Kusumoto Kasei Co., Ltd.) A red fluorescent paint composed of 1.50 toluene 30.00 121.50 was adjusted to a viscosity of 10 poise.

A coating speed of 7 m / min and a wet film thickness of 150 were applied on the composite ultraviolet absorbing layer using a knife coater.
5 minutes 4 in a drying oven coated at 120m
A fluorescent colored layer having a dry film thickness of 60 μm was formed by passing through for 0 seconds.

Next, as a reflective layer, parts by weight of Thermolac EM (40% acrylic resin toluene solution, manufactured by Soken Chemical Industry Co., Ltd.) 100.00 Titanium oxide R-650 (manufactured by Sakai Chemical Industry Co., Ltd.) 35.00 Antitera-U (dispersant) Manufactured by BYK Chemie) 1.50 Toluene 30.00 166.50 White paint was adjusted to a viscosity of 10 poise.

A coating speed of 11 m / min and a wet film thickness of 60 μ were applied on the fluorescent coloring layer using a reverse roll coater.
3 minutes 4 in a drying oven maintained at 120 ° C
A white reflective layer having a dry film thickness of 22 μm is formed by passing it through 0 seconds,
A fluorescent sheet having a total film thickness of 98 μm and having excellent weather resistance and sheet strength was obtained.

[0039]

According to the present invention, it is possible to provide a fluorescent sheet which has high saturation and high weather resistance, is thin, and can be used as a signboard, a sticker or the like after the adhesive processing.

Claims (1)

[Claims] 1. An ultraviolet absorbing layer comprising (A) a film having a visible light transmittance of 70% or more, an ultraviolet light transmittance of 0 to 30% and a film thickness of 5 to 150 μm, on which (B) a film thickness of 50.
A fluorescent sheet having a fluorescent coloring layer of ˜200 μm and a reflection layer (C) having a hiding ratio of 70% or more and a thickness of 5 to 50 μm.