JPH0635402A - Elapsed timedisplay label and its usage - Google Patents

Abstract

PURPOSE:To display the elapsed time of several minutes-several months by sticking a period elapse display layer, constituted by sticking a transparent protection film, a concealing layer, a dye diffusing layer, and an adhesive layer in order, on image receiving paper where a dye image is printed. CONSTITUTION:The period display label 1 consists of the transparent protection film 11, the concealing layer 12, the dye diffusing layer 13, the adhesive layer 14, and a peel layer 15. The concealing layer 12 consists of a white, yellow, red, or blue dye, a plasticizer, and a macromolecule bonding agent. The dye diffusing layer 13 consists of a black dye, a plasticizer, and a macromolecule bonding agent. Control over the diffusion of the dyes is adjusted with the amount of added plasticizers. The peel layer 15 is peeled and the adhesive layer 14 is stuck on the image receiving paper 2 where a dye image 21 is previously printed. Then the dye image 21 is diffused corresponding to the diffusion capacity of the composition of the dye diffusion layer 13 which is previously designed. Consequently, the period of several minutes-several months can be displayed as a visible image on the surface side of the transparent protection film 11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lapse display label, and in particular, has a limited effective period of X-ray-sensitive films, photographic papers, photosensitive papers, cosmetics, batteries, oils, chemicals and the like. It is applied to a product or a time-limited entry certificate etc. with anti-counterfeiting, and it can be seen at a glance whether it is within its validity period label (hereinafter referred to as "time indicator" or simply "indicator"). Call).

[0002]

2. Description of the Related Art The following is a method of expressing the period such as the expiration date of a product. For example, in a volatile drug, the active ingredient may be in the form of a solution or wax, and volatilization of these may be visually observed 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 are indicators that use the volatility of the substance as an indicator of the period, and the degree of coloring decreases due to volatilization of colored liquids (including those absorbed in gel) and volatilization of sublimable dyes. There is something to see. However, the volatilization of substances is greatly affected by temperature and humidity, and it is difficult to show an accurate period, and the volatilized substances may contaminate the surrounding air.

Other examples are light, temperature, humidity, or
A time indicator that can judge the elapsed period is also conceivable by a color change caused by gases such as oxygen (O ₂ ) and carbon dioxide (CO ₂ ) in the atmosphere.

However, light, temperature, humidity, etc.
Changes in our lives are so great that we have to use these
Im indicator before the scheduled time elapses
A color change may occur, or it may change even after the scheduled period.
If you do not do so, a stable time indication
Difficult to obtain In addition, a certain amount of oxygen permeability
Methylene blue in a bag made of plastic film
O in the atmosphere such as ₂Colorants that change color depending on the amount of
Put it in, seal it in a vacuum and seal this plastic over time.
O penetrating through the film₂By this colorant
To discolor and measure the elapsed time with it
Was also considered, but generally oxygen of plastic film
The amount of permeation changes depending on the ambient temperature and humidity.
A stable time that can always measure a certain period of time
Getting an indicator is difficult.

Furthermore, by 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 changing the color of the colorant by changing the pH, but this time indicator can not display the effective period of fragrance, deodorant or insect repellent, that is, the period of several months to several years, It has the drawback of discoloring in a short time (several hours to several tens of hours) and is sensitive to the influence of humidity, so it cannot be used as an indicator for displaying the elapsed time in such applications.

[0006]

For the purpose of solving the above problems, a stable period which can display the progress of a period of several minutes to several months and which is not affected by light humidity and other factors in the atmosphere. Proposal of progress indicator (Japanese Patent Application No. 4-185027)
did. The period indicator has a concealment and dye diffusion layer consisting of a pigment, a plasticizer, and a polymer binder on a transparent protective film, and an adhesive layer on the layer, and a release paper on the progress indicator layer. In the period display label, the label image is pasted on a period-lapse image paper including the dye image, and the dye image diffused on the transparent protective film surface side is displayed over time to display the elapsed period. . However, it is possible to display a clearly visible period for a few minutes to a few hours, but for a long period display of several months, the density of the dye image is low or the image is blurred, resulting in a lack of clearness. There was a problem.

Therefore, the present invention has been made in view of such problems, and the problem is that it is possible to visually and clearly display the progress of a long period of several minutes to several months, especially several months. Moreover, the object is to provide a stable time-lapse indicator which is not affected by light, humidity or other factors in the atmosphere.

[0008]

According to a first aspect of the present invention, release paper is pasted on a time-lapse display layer formed by sequentially laminating a hiding layer, a dye diffusion layer and an adhesive layer on a transparent protective film. It is a period elapsed display label characterized by being combined.

A second aspect of the present invention is a method for using the above-mentioned elapsed-age display label, which comprises sticking the label on an image-receiving paper on which a dye image is printed, and observing the transparent protective film surface side over time. A method of using a period elapsed display label, characterized in that a dye image diffused in the image is displayed to indicate the passage of time.

The principle of the present invention utilizes the diffusion of dyes, as is apparent from the components of the present invention. Since the control of the diffusion of the dye can be arbitrarily designed depending on the thickness of the dye diffusion layer, the type of the polymer binder and the addition amount of the plasticizer, it is possible to visually display an arbitrary period. Is.

The present invention will be described in detail below. FIG. 1 is a cross-sectional view of a period elapsed display label of the present invention. The time-lapse display label (1) comprises a transparent protective film (11), a hiding layer (12), a dye diffusion layer (13), an adhesive layer (14) and a peeling layer (15).

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

The hiding layer (12) used in the present invention is composed of a white, yellow, red or blue pigment, a plasticizer and a polymer binder. It is preferable that the pigment has a high hiding property. For example, titanium oxide, zinc oxide, lithopone,
Lead white, cadmium yellow, yellow lead, titanium yellow, zinc chromate, loess, chrome vermillion, red pigment, amber, yellow iron oxide, red iron oxide, cadmium let, dark blue, red tin, chrome oxide green, cobalt blue, ultramarine blue, cobalt Inorganic pigments such as violet and benzidine yellow, Hansa yellow, resolelet, alizarin lake, pigment scarlet 3B, brilliant carmine 6B, permanent red F-5R, lake red C, permanent red 4R, rhodamine lake B,
Rhodamine Rake Y, Para Red, Peacock Blue Rake, Phthalocyanine Blue, Permanent Yellow H
R, quinacridone, perinone perylene, chromophthal yellow 6G, chromophthal yellow 3G, chromophthal yellow GR, and other white, yellow, red, and blue pigments.

The plasticizer used in the present invention should be relatively sparingly volatile and compatible (compatible) with the polymeric binder used. Any such compound can be used. For example, phosphoric acid esters such as tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di2-ethylhexyl phthalate, phthalic acid. Diisononyl, dioctyldecyl phthalate, butylbenzyl phthalate and other phthalates, butyl oleate, glycerin monooleate and other aliphatic monobasic esters, dibutyl adipate, di-n-hexyl adipate,
Aliphatic dibasic acid esters such as di2-ethylhexyl adipate, alkyl 610 adipate, di2-ethylhexyl azelate, dibutyl sebacate, di2-ethylhexyl sebacate, diethylene glycol dibenzoate, triethylene glycol di2-ethyl butyral Dihydric alcohol ester such as acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, oxy acid ester such as tributyl acetyl citrate, chlorinated paraffin, methyl abietic acid, trimellitic acid plasticizer, polyester Plasticizer,
Examples thereof include epoxy plasticizers and stearic acid plasticizers.

As the polymer binder used in the present invention, any thermoplastic resin can be used. Examples of the thermoplastic resin include ester resins such as linear saturated polyester, 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 acid resin, methacrylic acid resin, epoxy resin, styrene-butadiene copolymer, styrene-acrylonitrile resin, petroleum resin, chlorinated polypropylene,
Examples thereof include polyamide resins, cellulose resins, polyvinyl alcohol resins, ionomer resins, ethylene-acrylic acid copolymers, polyurethane resins and the like. The thermoplastic resins described above may be used alone or in combination of two or more.

In the present invention, the composition ratio of each composition of the hiding layer is not limited, but the pigment for imparting the hiding property is 2 with respect to 100 parts by weight of the polymer binder from the viewpoint of suppressing the coating amount.
It is preferably used in the range of 00 to 500 parts by weight. The plasticizer may be 1 to 20 parts by weight. The coating amount is preferably 5 to 10 g / m ² in consideration of the hiding property.

The dye diffusion layer (13) used in the present invention is
It is composed of black pigment, plasticizer and polymer binder. The role of the dye diffusion layer is to diffuse the dye and to make the diffused dye invisible. The control of the diffusion of the dye is adjusted by the addition amount of the plasticizer, and making the dye visually invisible makes it concealed by the black pigment. Therefore, it is preferable that the black pigment has a high hiding property. Examples include carbon black and aniline black. Further, the pigments described in the above-mentioned hiding layer may be appropriately mixed and used as a black color.
Further, as the plasticizer and polymer binder used in the dye diffusion layer of the present invention, those described in the above-mentioned concealing layer can be similarly used.

In the present invention, the composition ratio of each composition of the dye diffusion layer is in the range of 200 to 500 parts by weight with respect to 100 parts by weight of the polymer binder for the black pigment, and 2 to 60 parts by weight for the plasticizer. Preference is given to using. The coating amount is preferably 2 to 30 g / m ² in consideration of the hiding property and the dye diffusing ability.

The adhesive layer (14) used in the present invention may be a commonly used adhesive. The adhesive is roughly classified into three types. Rubber, acrylic and silicone adhesives. These adhesives are elastic
It is composed of a tackifier, a plasticizer, and a filler auxiliary agent. Specifically, as the elastic body, natural rubber, synthetic isoprene, recycled rubber, SBR rubber, polyisoprene rubber, polyacrylic acid ester or its derivative, styrene-isoprene-styrene rubber, silicone rubber, silicone resin and the like are used. Tackifiers are rosin-based and rosin-derivatives, polyterpene resins, chroman-indene resins, petroleum-based resins, terpene-phenolic 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 pigment or an inorganic pigment and an antioxidant such as an antioxidant are added.

The coating amount of the adhesive layer of the present invention is preferably 5 to 25 g / m ² in consideration of the adhesive ability and the dye transfer ability.

The release layer (paper) used in the present invention may be any of those generally used. For example, it is a paper obtained by extrusion-coating polyethylene whose surface is coated with silicone, a kraft paper which is clay-painted and then spar calendered, a glassine paper, and various plastic films.

The label (1) for indicating the passage of time is first prepared by coating the hiding layer composition with a suitable solvent, and coating the coating on the transparent protective film (11) with a gravure coater, roll coater, bar coater, reverse coater, comma coater, The composition is applied and dried with a coating machine such as a die coater, and then the dye diffusion layer composition and the adhesive layer composition are each made into a coating material and applied, and a release paper is attached at the same time when the adhesive layer composition is applied. The method for coating the dye diffusion layer composition and the adhesive layer composition into a coating material and the coating method are the same as those for the hiding layer composition.

The time-lapse display label (1) thus obtained is peeled off from the peeling layer (15) and attached to the image receiving paper on which the dye image is printed in advance from the adhesive side. After pasting, 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 diffusing ability of the dye diffusion layer composition designed in advance. Dyes that can be used here include oil-soluble dyes and disperse dyes.
Specifically, for example, oil-soluble dyes include solvent yellow 2, solvent orange 1, solvent red 2
4, azo dyes such as Solvent Brown 3, Solvent Yellow 10, Solvent Orange 5, Solvent Brown 37, Solvent Orange 5, Solvent Red 8 and other azo metal complex salts, Solvent Violet 13, Solvent Blue 11, Solvent Green 3 and other anthraquinones Examples of the dye include phthalocyanine dyes such as Solvent Blue 25.

As disperse dyes, Disperse Orange 3, Disperse Red 1, Disperse Yellow 3, Disperse Violet 24, Disperse Blue 44
And other aminoazo dyes, Disperse Orange 11, Disperse Red 4, Disperse Violet 1, Disperse Blue 4 and other aminoanthraquinone dyes, Disperse Yellow 1 and 42, and utroarylamine dyes. Here, the disperse dye also includes a sublimation dye.

FIG. 2 shows an example in which the period elapsed 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 body on which a dye image is printed. (21) is a dye image.

[0026]

According to the present invention, a dye diffusion layer is obtained by laminating a transparent protective film, a concealing and dye diffusion layer and a time-lapse display label comprising an adhesive layer on the layer on an image receiving paper on which a dye image is printed. It is possible to display a visible image on the transparent film surface side for a period of several minutes to several months depending on the dye diffusing ability of.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, "part" indicates part by weight.

(Example 1) <Composition of hiding layer coating composition> Polyester resin 20 parts (Voyron 200 manufactured by Toyobo Co., Ltd.) Titanium oxide 50 parts Plasticizer 10 parts (Di-2-ethylhexyl sebacate) Toluene / 2- Butanone (2/1) 80 parts

<Composition of Dye Diffusion Layer Coating> Vinyl chloride-vinyl acetate copolymer 20 parts (Sekisui Chemical Co., Ltd. S-REC C) Carbon black 10 parts Plasticizer (dioctyl phthalate) 10 parts Toluene / 2-butanone ( 1/2) 80 copies

<Composition of Adhesive Layer Paint> One-component solvent-based acrylic adhesive 10 parts Toyo Ink Mfg. Co., Ltd. Olivine BPS4627-36T Solid content 36 wt% Solvent ethyl acetate / toluene ethyl acetate / toluene (1/1) 10 copies

The above concealing layer coating composition obtained by uniformly dispersing in a sand mill on a transparent polyester film having a thickness of 35 μm was dried with a wire bar to give a dry weight of 7 g /
It was coated and dried so as to have m ² to obtain a hiding layer. The dye diffusion layer coating material was applied onto the layer using a wire bar so as to have a dry weight of 2 g / m ² and dried to form a dye diffusion layer. Further, the adhesive layer coating material was applied and dried on the layer using a wire bar so that the dry weight was 5 g / m ² , and an adhesive layer was provided to obtain a time-lapse display layer. A release paper was attached on the layer to produce a time-lapse label.

Example 2 As a composition for a hiding layer, permanent red 4 which is an organic pigment instead of titanium oxide is used.
It is substantially the same as the period display label according to Example 1 except that R is applied.

(Example 3) This is substantially the same as the period display label according to Example 1 except that a plasticizer (dioctyl phthalate) is applied to 4 parts as a hiding layer coating material and a dye diffusion layer coating material.

(Example 4) <Composition of hiding layer coating composition> Vinyl chloride-vinyl acetate copolymer 20 parts (Sekisui Chemical Co., Ltd. Elek C) Polyester resin 2 parts (Unitika Co., UE-3200) Titanium oxide 40 parts Plasticizer (dioctyl phthalate) 2 parts Toluene / 2-butanone 80 parts

<Composition of Dye Diffusion Layer Paint> Polyester resin 20 parts (Toyobo Co., Ltd. Byron-300) Carbon black 10 parts Plasticizer (dioctyl phthalate) 2 parts Toluene / 2-butanone (2/1) 80 parts

<Composition of Adhesive Layer Paint> Synthetic Rubber Adhesive manufactured by Toyo Ink Mfg. Co., Ltd. Olivine BPS3757-1 Solid content: 27% by weight Solvent: Toluene / n-hexane / acetone

Transparent polyester film with a thickness of 35 μm
It is made by evenly dispersing in a sand mill in advance.
Drying weight of the concealing layer paint using wire bar is 10g
/ M ²Was coated and dried to obtain a hiding layer. That layer
Using the wire bar above the dye diffusion layer, dry weight
Is 3 g / m²Coating and drying to form a dye diffusion layer
It was Further, apply the above adhesive layer paint on that layer with a wire bar
Use dry weight of 5g / m²It is applied and dried so that
A coating layer was provided to obtain a time-lapse display layer. Release paper on that layer
Were pasted together to produce a time-lapse display label.

(Example 5) <Composition of hiding layer coating composition> Polyester resin 20 parts (Toyobo Co., Ltd. K588) Titanium oxide 40 parts Plasticizer (diocterphthalate) 1 part Toluene / 2-butanone (1/1) 80 copies

<Composition of Dye Diffusion Layer Coating Composition> Methyl methacrylate-methacrylic acid ester copolymer 20 parts (Mitsubishi Rayon Co., Ltd. Dianal BR-60) Carbon black 10 parts Plasticizer (dioctelphthalate) 1.5 Parts Toluene / 2-butanone (1/1) 80 parts

<Composition of Adhesive Layer Paint> Acrylic Ester Adhesive manufactured by Toyo Ink Mfg. Co., Ltd. Olivine BPW5449 Solid content 60% by weight Solvent water

On a transparent polyester film having a thickness of 35 μm, the above concealing layer coating composition, which was previously uniformly dispersed in a sand mill, was dried with a wire bar to give a dry weight of 10
It was coated and dried so as to be g / m ² to obtain a hiding layer. An adhesive layer was provided on the layer by coating and drying the above dye diffusion layer coating material using a wire bar so that the dry weight was 10 g / m ² . Further, the adhesive layer coating material was applied and dried on the layer using a wire bar so that the dry weight was 5 g / m ² , and an adhesive layer was provided to obtain a time-lapse display layer. A release paper was attached on the layer to produce a time-lapse label.

(Comparative Example 1) <Composition of hiding layer and dye diffusion layer paint> Methacrylic acid-methacrylic acid ester copolymer 20 parts (Mitsubishi Rayon Co., Ltd., Diamer BR-60) Polyester resin 3 parts (Unitika ( UE-3200) Titanium oxide 40 parts Plasticizer (dimethyl phthalate) 1.5 parts Toluene / 2-butanone 80 parts

<Composition of Adhesive Layer Paint> Acrylic Ester Adhesive Toyo Ink Mfg. Co., Ltd. Olivine BPW5449 Solid content 60% by weight Solvent water

On the transparent polyester film having a thickness of 35 μm, the above-mentioned concealing and dye-diffusing layer, which was uniformly dispersed by an attritor, was coated and dried using a wire bar so that the dry weight was 30 g / m ^2. To obtain a hiding and dye diffusion layer. The adhesive layer coating composition was applied to 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 to obtain a period indicating layer. A release paper was attached to the layer to produce a time-lapse display label.

(Evaluation) The release paper of the time-lapse display labels obtained in Examples 1 to 4 and Comparative Example 1 was peeled off, and a blue oil-soluble dye (Solvent Blue 25 manufactured by Hodogaya Chemical Co., Ltd.) was printed in advance. A label is attached to the image receiving paper from the adhesive layer side, and the elapsed time of the saturation concentration of the dye image diffused to the transparent protective film side of the produced label is measured using a reflection densitometer of RD-918 manufactured by Macbeth. did. The measured results are shown in Table 1. As is clear from Table 1, it is possible to arbitrarily display the passage of time by changing the composition of the hiding and dye diffusion layers.

[0046]

[Table 1]

* Evaluation atmosphere temperature: 20 ° C. * Blue dye image density: 1.98

[0048]

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

Further, the diffusion speed of the dye can be arbitrarily controlled by the thickness of the dye diffusion layer, the kind of the polymer binder and the addition amount of the plasticizer.

[0050]

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing the structure of a period elapsed label according to an embodiment.

FIG. 2 is a cross-sectional view showing a structure of a period elapsed display body according to the embodiment.

[Explanation of symbols]

 1 Time-lapse display label 2 Image receiving paper on which dye image is printed 11 Transparent protective film 12 Concealment layer 13 Dye diffusion layer 14 Adhesive layer 15 Release layer 21 Dye image

Claims (4)

[Claims] 1. A time-lapse display label comprising a release paper laminated on a time-lapse display layer formed by sequentially laminating a hiding layer, a dye diffusion layer and an adhesive layer on a transparent protective film. 2. The label according to claim 1, wherein the hiding layer comprises a white, yellow, red or blue pigment, a plasticizer and a polymer binder. 3. The label according to claim 1, wherein the dye diffusion layer comprises a black pigment, a plasticizer and a polymer binder. 4. A method of using a time-lapse display label, which comprises laminating release paper on a time-lapse display layer formed by sequentially laminating a hiding layer, a dye diffusion layer and an adhesive layer on a transparent protective film, Of the label showing the elapsed period, which is characterized in that the label is pasted on the image receiving paper on which the dye image is printed and the diffused dye image is displayed on the transparent protective film surface side over time. how to use.