JP3014543B2 - Time-lapse display label and how to use it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a label indicating the passage of time, and more particularly to a label which is sensitive to X-rays, such as a film, a photographic paper, a photosensitive paper, a cosmetic, a battery, an oil, and a chemical. A time-lapse display label (hereinafter referred to as “time indicator” or simply “indicator”) that can be applied to products or time-limited introductory certificates to which counterfeiting has been granted, so that it is possible to know at a glance whether they are within the validity period. Call).

[0002]

2. Description of the Related Art As a method of expressing a period such as an expiration date of a product, there is the following method. For example, in some volatile drugs, the active ingredient is in the form of a solution or wax, and the volatilization of these can be seen from the outside of the container. This type cannot be applied to all products because the properties of the active ingredient itself are limited to volatile ones. Regardless of the active ingredient, there is an indicator that indicates the period using the volatility of the substance, which reduces the degree of coloring due to the volatilization of the colored liquid (including those absorbed in the gel) and the volatilization of the sublimable dye. There is something to see. However, the volatilization of the substance is greatly affected by the temperature and the humidity, and it is difficult to show an accurate period, and the volatile substance may pollute the surrounding air.

[0003] Other examples include light, temperature, humidity or
A time indicator is also conceivable in which the elapsed period can be determined by a color change due to a gas such as oxygen (O ₂ ) or carbon dioxide (CO ₂ ) in the atmosphere.

[0004] However, light, temperature, humidity, etc. change greatly in daily life, so that a time indicator using them may cause a color change before the scheduled period elapses or the scheduled period elapses. After that, the color does not change, and it is difficult to obtain a stable time indicator. In addition, a colorant such as methylene blue, which changes color depending on the amount of O _{2 in} the atmosphere, is put in a bag made of a plastic film having a certain amount of oxygen permeability, and sealed in a vacuum state. A method of discoloring the colorant by penetrating O ₂ and measuring the elapsed time was also studied. However, in general, the amount of oxygen permeation of a plastic film changes depending on the ambient temperature and humidity. Therefore, it is difficult to obtain a stable time indicator that can always measure the elapse of a certain period.

Further, using CO ₂ instead of O ₂ ,
A bag made of plastic film having a certain amount of carbon dioxide gas permeability, and sealed under vacuum put colorant color change by a change in pH in the atmosphere, the atmosphere due to CO ₂ entering passes through the plastic film There is also a method of discoloring the colorant by changing the pH, but this time indicator cannot display the validity period of the fragrance, deodorant, or insect repellent, that is, the period of several months to several years, It has the disadvantage of discoloring in a short time (several hours to several tens of hours), and is sensitive to the influence of humidity, so that it cannot be used as an indicator for indicating the passage of time in such applications.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such a problem, and an object thereof is to display the progress of a period of several minutes to several months.
An object of the present invention is to provide a stable time-lapse indicator that is not affected by light, humidity, and other atmospheric factors.

[0007]

According to the first aspect of the present invention, there is provided a concealing and dye diffusing layer comprising a pigment, a plasticizer and a polymer binder on a transparent protective film, and an adhesive layer on the layer. A period elapse display label which displays the elapse of time by a change in the density of a dye image obtained by laminating a release paper on a formed period elapse display layer.

According to a second aspect of the present invention, there is provided a hiding and dye diffusion layer comprising a pigment, a plasticizer, and a polymer binder on a transparent protective film, and a time-lapse display comprising an adhesive layer on the dye diffusion layer. A method for using a time-lapse display label, characterized in that a release paper is laminated on a layer, and the label is laminated on an image receiving paper on which a dye image is printed, and the transparent film surface side with time. Density of dye image diffused to
This is a usage method of a period elapse display label, which is characterized by displaying a change and displaying a period elapse.

The principle of the present invention utilizes the diffusion of a dye as is apparent from the components of the present invention. The control of the diffusion of the dye can be arbitrarily designed depending on the thickness of the concealing and dye diffusion layer, the type of the polymer binder and the amount of the plasticizer added, so that any period can be visually displayed. Is what you do.

Hereinafter, the present invention will be described in detail. FIG. 1 is a sectional view of a period elapse display label of the present invention. The period elapse label (1) comprises a transparent protective film (11), a concealing and dye diffusion layer (12), an adhesive layer (13), and a release layer (14).

The transparent protective film (1) used in the present invention
1) Any plastic film generally used can be used. For example, cellophane, acetate, vinyl chloride, polyethylene, polypropylene, polyester, ethylene tetrafluoride, vinyl fluoride,
Films such as polyimide, polycarbonate, and polystyrene.

The hiding and dye diffusion layer (12) used in the present invention is composed of a pigment, a plasticizer and a polymer binder. Pigments having high concealing properties are preferred. For example, titanium oxide, zinc oxide, lithopone, lead white, cadmium yellow, graphite, titanium yellow, zinc chromate, loess,
Inorganic pigments such as chromium vermilion, red pigment, amber, yellow iron oxide, red iron oxide, cadmium red, navy blue, lead red, chromium green, cobalt blue, ultramarine, cobalt violet, iron black, etc. and benzidine yellow, Hansa yellow, lithol Lett, Alizarin Lake, Pigment Scarlet 3B, Brilliant Carmine 6B,
Permanent red F-5R, lake red C, permanent red 4R, rhodamine lake B, rhodamine lake Y, para red, peacock blue lake, phthalocyanine blue, aniline black, permanent yellow HR, quinacridone, perinone perylene, chromophtal yellow 6G, Organic pigments such as Chromophtal Yellow 3G and Chromophtal Yellow GR. Particularly preferred are the above-mentioned pigments such as white, yellow, red and blue.

The plasticizer used in the present invention must be relatively involatile and have an affinity (compatibility) with the polymeric binder used. Any such compounds can be used. For example, phosphates such as tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, phthalic acid Diisononyl, dioctyldecyl phthalate, phthalic acid esters such as butylbenzyl phthalate, butyl oleate, aliphatic monobasic acid esters such as glycerin monooleate, dibutyl adipate, di-n-hexyl adipate;
Aliphatic dibasic acid esters such as di-2-ethylhexyl adipate, alkyl adipate 610, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyral Oxyacid esters such as dihydric alcohol esters such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, and tributyl acetyl citrate; chlorinated paraffins; methyl abietic acid; trimellitic acid plasticizers and polyesters Plasticizer,
Epoxy plasticizers, stearic acid plasticizers and the like.

As the polymer binder used in the present invention, any thermoplastic resin can be used. For example, ester resins such as linear saturated polyester as a thermoplastic resin, vinyl chloride resins such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, vinyl acetate resin, styrene resin, butyral resin ,
Acrylic resin, methacrylic resin, epoxy resin, styrene-butadiene copolymer, styrene-acrylonitrile resin, petroleum resin, chlorinated polypropylene,
Examples thereof include a polyamide resin, a cellulose resin, a polyvinyl alcohol resin, an ionomer resin, an ethylene-acrylic acid copolymer, and a polyurethane resin. The above-mentioned thermoplastic resins can be used alone or in combination of two or more.

In the present invention, the composition ratio of each composition of the hiding and dye diffusion layers is not limited, but the plasticizer for controlling the diffusion of the dye is used in the range of 0 to 60 parts by weight with respect to 100 parts by weight of the solid content. Is preferred. The coating amount is preferably 5 to 50 g / m ² in consideration of the hiding property and the dye diffusing ability.

The pressure-sensitive adhesive layer (13) used in the present invention comprises:
Commonly used adhesives can be used. The adhesive is
They are roughly classified into three types. Rubber-based, acrylic-based, and silicone-based adhesives. These pressure-sensitive adhesives are composed of auxiliary substances such as an elastic body, a tackifier, a plasticizer, a filler, and an antioxidant. Specifically, natural rubber, synthetic isoprene, recycled rubber, SBR rubber, polyisoprene rubber, polyacrylate, or a derivative thereof, styrene-isoprene-styrene rubber, silicone rubber, silicone resin, etc. are used as the elastic body. Tackifiers include rosin and rosin derivatives, polyterpene resins, chroman-indene resins, petroleum resins, terpene phenol resins and the like. Examples of the plasticizer include liquid polybutene, mineral oil, lanolin, liquid polyisoprene, and liquid polyacrylate. If necessary, a filler such as an extender or an inorganic pigment or an antioxidant such as an antioxidant is added.

The coating amount of the pressure-sensitive adhesive layer of the present invention is preferably from 5 to 25 g / m ² in consideration of the adhesiveness and dye transferability.

The release layer (14) used in the present invention can be any of those generally used.
For example, paper extruded and coated with polyethylene coated on the surface with silicone, kraft paper, glassine paper, various plastic films, etc., which have been subjected to spar calendering after clay coating.

The time-lapse label (1) is prepared by first applying a coating to the concealing and dye-diffusing layer composition with an appropriate solvent, and applying the coating on a permeable protective film (11) by a gravure coater, roll coater, bar coater, reverse coater. The composition is applied and dried with a coating machine such as a comma coater or a die coater, and then the pressure-sensitive adhesive layer composition is formed into a paint and applied, and at the same time, a release paper is attached. The method for preparing the coating composition and applying the pressure-sensitive adhesive layer composition is the same as that for the hiding and dye diffusion layer composition.

The label for elapse of time (1) thus obtained is peeled off from the release layer (14) and adhered from the surface of the pressure-sensitive adhesive layer (13) on an image receiving paper on which a dye image is printed in advance. After lamination, a period of several minutes to several months can be displayed as a visible image on the transparent protective film (11) side depending on the previously designed concealment and diffusion ability of the dye diffusion layer composition. Dyes usable here include oil-soluble dyes and disperse dyes. Specifically, examples of the oil-soluble dye include azo dyes such as Solvent Yellow 2, Solvent Orange 1, Solvent Red 24, and Solvent Brown 3, Solvent Yellow 10, Solvent Orange 5, Solvent Brown 37, Solvent Orange 5, and Solvent Red. And anthraquinone dyes such as Solvent Blue 25, and phthalocyanine dyes such as Solvent Blue 25.

Disperse dyes include Disperse Orange 3, Disperse Red 1, Disperse Yellow 3, Disperse Violet 24, Disperse Blue 44
And aminoanthraquinone dyes such as Disperse Orange 11, Disperse Red 4, Disperse Violet 1 and Disperse Blue 4, and utroarylamine dyes such as Disperse Yellow 1 and 42. Here, the disperse dye includes a sublimation dye.

FIG. 2 shows an example in which the period elapse display label (1) shown in FIG. 1 is pasted on an image receiving paper on which a dye image is printed. (2) is an image receiving paper main body on which a dye image is printed. (21) is a dye image.

[0023]

According to the present invention, a time-lapse display label comprising a transparent protective film, a concealing and dye-diffusing layer and an adhesive layer on the transparent protective film, is attached to an image-receiving paper on which a dye image is printed, thereby providing concealing and concealing. Depending on the dye diffusing ability of the dye diffusion layer, a period of several minutes to several months can be displayed as a visible image on the transparent film surface side.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. In the examples, "parts" indicates parts by weight.

(Example 1) <Composition of Hiding and Dye Diffusion Layer Coating> 20 parts of vinyl chloride-vinyl acetate copolymer (Eslec C manufactured by Sekisui Chemical Co., Ltd.) 2 parts of polyester resin (UE manufactured by Unitika Ltd.) -3200) Titanium oxide 40 parts Plasticizer 10 parts (Dioxyl phthalate) Toluene / 2-butanone (1/2) 80 parts

<Composition of Pressure-sensitive Adhesive Layer Paint> One-part solvent-based acrylic pressure-sensitive adhesive 10 parts Toyo Ink Mfg. Co., Ltd. Olivine BPS4627-36T Solid content: 35% by weight Solvent: ethyl acetate / toluene ethyl acetate / toluene (1 / 1) 10 copies

The above concealing and dye-diffusing layer paint, which has been uniformly dispersed in advance by a sand mill on a 35 μm-thick transparent polyester film, is coated and dried to a dry weight of 10 g / m ² using a wire bar. Thus, a hiding and dye diffusion layer was obtained. On the layer, the above-mentioned adhesive layer coating material was applied using a wire bar and dried so as to have a dry weight of 7 g / m ² to provide an adhesive layer to obtain a time-lapse display layer.
A release paper was stuck on the layer to produce a time-lapse display label.

(Example 2) As the composition for the concealing layer and the dye diffusion layer, the same as the period elapse display label according to Example 1 except that permanent red 4R which is an organic pigment was used instead of titanium oxide. is there.

Example 3 The label is almost the same as that of Example 1, except that a plasticizer (dioctyl phthalate) is applied to 4 parts of the composition for the concealing layer and the dye diffusion layer.

(Example 4) <Composition of Hiding and Dye Diffusion Layer Coating> Polyester resin 20 parts (Toyobo Co., Ltd. Byron 103) Titanium oxide 50 parts Plasticizer 2 parts (di-2-ethylhexyl sebacate) Toluene 80 parts of 2-butanone (2/1)

<Composition of pressure-sensitive adhesive layer coating> Synthetic rubber-based pressure-sensitive adhesive Toyo Ink Mfg. Co., Ltd. Olivine BPS3757-1 Solid content: 27% by weight Solvent: toluene / n-hexane / acetone

On a transparent polyester film having a thickness of 35 μm, the above-mentioned concealing and dye-diffusing layer paint, which has been uniformly dispersed in advance by an attritor, is applied using a wire bar so as to have a dry weight of 20 g / m ^2. Drying gave a hiding and dye diffusion layer. On the layer, the above-mentioned adhesive layer coating material was applied using a wire bar and dried so as to have a dry weight of 10 g / m ² to provide an adhesive layer to obtain a time-lapse display layer. A release paper was stuck on the layer to produce a time-lapse display label.

Example 5 <Composition of Hiding Layer and Dye Diffusion Layer Coating Material> 20 parts of methyl methacrylate-methacrylate copolymer (Diamer BR-60 manufactured by Mitsubishi Rayon Co., Ltd.) 3 parts of polyester resin (Unitika) (UE-3200 manufactured by Co., Ltd.) Titanium oxide 40 parts Plasticizer (dimethyl phthalate) 1.5 parts Toluene / 2-butanone 80 parts

<Composition of pressure-sensitive adhesive layer coating> Acrylic ester-based pressure-sensitive adhesive Toyo Ink Manufacturing Co., Ltd. Olivine BPW5449 Solid content 60 Solvent Water

The above-mentioned concealing and dye-diffusing layer dye, which is uniformly dispersed in advance by an attritor, on a 35 μm-thick transparent polyester film, is coated with a wire bar and dried to a dry weight of 30 g / m ^2. Thus, a hiding and dye diffusion layer was obtained. The adhesive layer paint was applied on the layer using a wire bar so as to have a dry weight of 20 g / m ² and dried to form an adhesive layer, thereby obtaining a period display layer. A release paper was stuck on the layer to produce a time-lapse display label.

(Evaluation) The release paper of the label indicating the passage of time obtained in Examples 1 to 5 was peeled off, and on an image receiving paper on which a blue oil-soluble dye (Solvent Blue 25 manufactured by Hodogaya Chemical Industry Co., Ltd.) was previously printed. The label is adhered from the pressure-sensitive adhesive layer side, and the elapsed time of the saturation concentration of the dye image diffused to the transparent protective film surface side of the prepared label is determined by Macbeth RD.
It measured using the reflection densitometer of -918. Table 1 shows the measurement results. As is apparent from Table 1, by changing the composition of the concealment and dye diffusion layers, it was possible to arbitrarily display the passage of time.

[0037]

[Table 1]

* Evaluation atmosphere temperature: 20 ° C. * Density of blue dye image: 1.98

[0039]

According to the present invention, a transparent protective film, a concealing and dye-diffusing layer, and a time-lapse display layer comprising a pressure-sensitive adhesive layer on the layer are laminated on an image receiving paper on which a dye image is printed. It is possible to provide a stable time-lapse display body that can display the progress of a period of several minutes to several months and is not affected by light, humidity, and other atmospheric factors.

The diffusion speed of the dye can be arbitrarily controlled by the thickness of the concealing and dye diffusion layer, the type of the polymer binder and the amount of the plasticizer added.

[0041]

[Brief description of the drawings]

FIG. 1 is a configuration sectional view of a period elapse display label according to an embodiment.

FIG. 2 is a configuration sectional view of a period elapse display body according to the embodiment.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 period elapse label 2 image receiving paper on which dye image is printed 11 transparent protective film 12 concealment and dye diffusion layer 13 adhesive layer 14 release layer 21 dye image

Claims (2)

(57) [Claims] An opaque and dye diffusion layer comprising a pigment, a plasticizer and a polymer binder on a transparent protective film and a pressure-sensitive adhesive layer provided on the opaque and dye diffusion layer. The period elapses due to the change in the density of the dye image
A time-lapse display label characterized by being displayed. 2. A concealing and dye-diffusing layer comprising a pigment, a plasticizer and a polymer binder on a transparent protective film and a pressure-sensitive adhesive layer provided on the opaque and dye-diffusing layer. A method of using a time-lapse display label, characterized in that the label image is adhered to the image receiving paper on which the dye image is printed, and the label image is diffused with time over the transparent film surface side. A method of using a period elapse display label, wherein a period change is displayed by displaying a change in density of the image.