JP2002129139A - Discolorable time lapse indicator and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a discolorable time lapse indicator that can exhibit discoloration performances in response to environmental conditions (temperature and humidity) for a long term and to a lapse of time and can undergo distinct discoloration. SOLUTION: There is provided a discoloration time lapse indicator having a discolorable ink layer that discolors in response to temperature and/or humidity and to a lapse of time and a non-discolorable ink layer on a substrate, wherein a separation layer separates the support from the discolorable ink layer and the non-discolorable ink layer, the discolorable ink layer and the non-discolorable ink layer are formed in such a manner that at least a part or the whole of the discolorable ink layer is exposed to atmospheric air.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a discoloration time-lapse indicator and a method for producing the same.

[0002]

2. Description of the Related Art Products such as insect repellents and deodorants are stored in a storage location of the product and environmental conditions (temperature and humidity) in a room at the time of use.
And the time (elapsed time) in the environment changes its quality and function. Therefore, in order to control the quality of these products, an indicator for accurately grasping the atmospheric conditions in which the products are placed is required.

Conventionally, such a time indicator includes, for example, a heating time consisting of an electron-donating organic compound which exhibits a deep color upon heating, a dye which melts and evaporates with time, and a resin having an acidic group such as sulfonic acid or carboxylic acid. A progress indicator is known (Japanese Patent Publication No. 62-44590).

However, this display has the following problems. That is, there are problems such as the reaction to heat only, the use for a short period of time of about several hours to several days, and the difficulty of confirming discoloration.

On the other hand, a first layer and a second layer adjacent to each other and, if necessary, a third layer are provided on a substrate,
(1) the first layer is a layer containing a cyanine dye and an oil-soluble resin having a carboxyl group or a phenolic hydroxyl group as essential components, and if necessary, a fixing dye and a thickening resin; The layer is a layer containing a resin having a pH of 7 or more as an essential component as an emulsion and optionally containing a thickening resin. (3) The third layer has a high hygroscopicity that is soluble in water and / or aliphatic alcohols. Discoloration time-lapse indicator characterized by being a layer containing a molecule (Japanese Patent Laid-Open No. 5-1)
No. 26969). According to this technique, it can be used for a long period of time, up to about one week to two years.

However, in this technique, the discoloration (color difference) or visibility in the discoloration layer is not always sufficient, and there is room for improvement in this respect.

[0007]

SUMMARY OF THE INVENTION Accordingly, a main object of the present invention is to provide a discoloration performance in accordance with environmental conditions (temperature and / or humidity) and elapsed time for a long period of time,
It is an object of the present invention to provide a discoloration time-lapse indicator capable of confirming discoloration more clearly.

[0008]

Means for Solving the Problems The present inventor has conducted intensive studies in view of the problems of the prior art, and as a result, has found that the above object can be achieved by a discolorable time-lapse indicator having a specific structure. It was completed.

That is, the present invention relates to the following discoloration time-lapse indicator and a method for producing the same.

[0010] 1. A discoloring time-lapse indicator having a discoloring ink layer and a non-discoloring ink layer that changes color according to temperature and / or humidity and elapsed time on a substrate, wherein the substrate is separated from the discoloring ink layer and the non-discoloring ink layer. A color-changing time indicator comprising a color-changing ink layer and a non-color-changing ink layer formed on the color-separating layer such that a part or all of the color-changing ink layer is exposed to the outside air.

2. A method for producing a discoloration time-lapse indicator, comprising: forming an isolation layer on a substrate with an aqueous ink having an ink pH of 7 or more, and then forming a discoloration ink layer on the isolation layer with the discoloration ink.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Discoloration chronological indicator The discoloration chronological indicator of the present invention is a discolorable chronological indicator having a color-change ink layer and a non-color-change ink layer that changes color according to temperature and / or humidity and elapsed time on a substrate. A separating layer that separates the material from the color-changing ink layer and the non-color-changing ink layer; a color-changing ink layer and a non-color-changing ink layer are formed on the separating layer so that a part or all of the color-changing ink layer is exposed to the outside air; It is characterized by having. (1) Layer structure of the color-change ink layer and the non-color-change ink layer The color-change ink layer and the non-color-change ink layer are formed on the separation layer so that a part or the whole of the color-change ink layer is exposed to the outside air. Therefore, the color-change ink layer and the non-color-change ink layer may be formed in any form as long as the color-change ink layer is exposed to the outside air (atmosphere). For example, a configuration in which a color-changing ink layer is formed on the entire surface of the isolation layer, and a non-color-changing ink layer is formed on a part of the color-changing ink layer. Any pattern such as a configuration in which a non-color-changing ink layer is formed on other portions can be adopted.

In this case, the non-color-changing ink layer and the color-changing ink layer can be combined to form the non-color-changing ink layer and the color-changing ink layer so as to form characters, numerals, figures, and other designs. For example, as shown in the embodiment, if the non-color-changed ink layer and the color-changed ink layer are formed so that characters indicating the completion of detection appear with time, the color change can be easily and reliably recognized.

In the present invention, it is particularly preferable that a color changing ink layer is formed on a part of the separating layer and a non-color changing ink layer is formed on another part of the separating layer. That is, it is preferable that the non-color-change ink layer is formed so as not to overlap with the color-change ink layer. By employing such a configuration, the discoloration can be visually recognized more reliably. In such a configuration, more preferably, the color-changed ink layer and the non-color-changed ink layer before the color change have substantially the same color, and the color difference between the color-changed ink layer and the non-color-changed ink layer only after the color-changed ink layer has changed color. Is formed to appear. Thereby, the difference between before and after the discoloration can be grasped more clearly. (2) Components of Discoloration Aging Indicator The type of substrate is not particularly limited, and known materials can be applied. For example, metal and alloy materials (aluminum foil, stainless steel foil, tin foil, tin foil, etc.), plastics (polyester, cellophane, acetylcellulose, ethylcellulose, polyethylene, polypropylene, polyvinyl chloride, hydrochloric acid rubber, polystyrene, polycarbonate, polyvinyl alcohol) , Polyvinyl fluoride, polyamide,
Films or molded products such as polyfluoroethylene), fibers (paper, woody materials, nonwoven fabrics, woven fabrics, and other fiber sheets), inorganic materials (ceramics, glass, concrete, plasters), and composite materials thereof Can be used.

The color-changing ink layer is not limited as long as it changes color according to temperature and / or humidity and elapsed time, and the same color-changing ink layer (color-changing layer) in a known time-lapse indicator may be used. it can.

In particular, in the present invention, 1) at least one of a methine dye and a cyanine dye (both are collectively referred to as "dye") and 2) an oil-soluble resin having a carboxyl group and / or a phenolic hydroxyl group. It is preferable to use a discoloration ink layer that contains.

Known or commercially available methine dyes and cyanine dyes can be used. For example, C.
I. Basic Yellow 11, 12, 13, 14, 21,
22, 23, 24, 28, 29, 33, 35, 40, 4
3, 44, 45, 48, 49, 51, 52, 53, CI
Basic Red 12, 13, 14, 15, 27, 3
5, 36, 37, 45, 48, 49, 52, 53, 6
6, 68, CI Basic Violet 7, 15, 1
6, 20, 21, 39, 40, CI Basic Orange 27, 42, 44, 46, CI Basic Blue 62,
63 and the like. Among these, solubility is good,
CI basic yellow 11, 13, CI basic red 12, in terms of good coloring and decoloring properties,
13, 14, 15, 37, CI basic violet 15, 16 and the like can be suitably used.

The content of the dye in the color-changing ink layer may be appropriately determined according to the type of the dye to be used, the desired detection accuracy, and the like, but is usually about 0.001 to 5% by weight, preferably 0.01% by weight. -5% by weight, more preferably 0.01-1% by weight.

Known or commercially available oil-soluble resins having a carboxyl group and / or a phenolic hydroxyl group can also be used. Each of the carboxyl group and the phenolic hydroxyl group may have one or more. Such oil-soluble resins include, for example, rosin-based resins such as gum rosin, hydrogenated rosin, polymerized rosin, ultra-light rosin, phenolic resins such as phenolic resins, alkylphenol resins, terpene phenolic resins, rosin-modified phenolic resins, and maleic acid. Resin, rosin-modified maleic resin,
Maleic resins such as styrene-maleic acid copolymers can be mentioned. Among these, ultra-light rosin, alkylphenol resin, styrene-maleic acid copolymer, etc. can be preferably used from the viewpoint that they have good solubility and can contribute to excellent decoloration.

The content of the oil-soluble resin in the discoloration ink layer is as follows:
It may be appropriately determined according to the type of the oil-soluble resin to be used, the desired detection accuracy, and the like, but is usually about 10 to 99% by weight, preferably 30 to 99% by weight.

The color changing ink layer may contain a fixing dye, if necessary. By blending fixing dye,
More clear discoloration can be caused. As the fixing dye, those which dissolve or disperse in an organic solvent and do not react under alkaline conditions can be preferably used. For example, CI
Direct Yellow 12, 27, 98, CI Direct Red 1, 4, 28, CI Direct Orange 8, 2
6, 29, CI Direct Brown 2, 44, 58, 1
06, 209, CI Acid Orange 74, CI Acid Red 111, CI Acid Blue 113, 117,
120, CI Acid Green 9, 19, 44, CI Acid Brown 13, CI Mordant Brown 19, C.I.
I. Disperse Red 9, CI Solvent Yellow 1
6, 21, 29, 56, 61, CI Solvent Orange 1, 2, 14, 37, 40, CI Solvent Red 1,
8, 23, 30, 49, 81, 82, 83, 84, 10
0, 109, 121, CI Solvent Violet 8,
21, 27, CI Solvent Brown 20, a processed pigment obtained by previously kneading an oil-soluble carrier resin and a color pigment. Here, examples of the oil-soluble carrier resin include polyvinyl butyral, rosin-based resin, ethyl cellulose, styrene-maleic acid copolymer, and the like. Further, as the coloring pigment, condensed azo yellow, disazo yellow, isoindoline yellow,
Examples include anthraquinone yellow, perinone orange, monoazo red, quinacridone red, perylene red, anthraquinone red, monoazo brown, dioxazine violet, phthalocyanine blue, selenium blue, and phthalocyanine green. Among these fixing dyes, CI Solvent Yellow 16, 2 and 4 are excellent in alkali resistance and solubility.
Preferred are 9, 61, CI Solvent Blue 5, 12, 70, and the above-mentioned processed pigments.

The content of the fixing dye may be appropriately set according to the kind of the fixing dye to be used and the like, but is usually about 1 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the oil-soluble resin. The weight may be used.

The isolation layer is substantially composed of a resin component. The resin component is not particularly limited, but those having particularly excellent water resistance are preferred. Examples of such a resin include an acrylic resin, an acrylate resin, an acrylate copolymer, a styrene-acrylic acid copolymer, a styrene-maleic acid copolymer, a styrene-butadiene copolymer, and a hydroxyl group. Urethane resin, epoxy resin, ethylene-vinyl acetate copolymer, rosin-modified maleic resin, and the like.

In the separating layer, extenders, thickeners, defoamers, leveling agents, pH adjusters, surfactants,
Known additives such as an ultraviolet absorber and an antioxidant may be blended.

As an isolating layer of the indicator of the present invention, the water contacted with the isolating layer has a pH of 7 or more (preferably 8 to 1).
0). By designing the separating layer so as to be in the above-mentioned pH range, it is possible to more reliably recognize discoloration. In order to set the pH to 7 or more, for example, an aqueous ink having a pH of 7 or more may be used as an aqueous ink for forming an isolation layer. The pH of the water in contact with the separating layer can be confirmed by measuring the pH of the water drop after dropping the water drop on the separating layer and leaving it for one hour, using a pH meter.

Examples of the extender include titanium oxide, calcium carbonate, magnesium carbonate, clay, talc, diatomaceous earth, white carbon, alumina white, bentonite and the like. The content of the extender pigment depends on the kind of the extender pigment to be used and the like, but is usually about 1 to 50% by weight, preferably 10 to 30% by weight in the separating layer.

Examples of the thickener include polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. The content of the thickener depends on the type of the thickener to be used, but is usually about 0.1 to 10% by weight, preferably 0.5 to 5% by weight in the separation layer.
It is good.

Examples of the defoaming agent include silicone-based and mineral oil-based defoaming agents. The content of the antifoaming agent depends on the type of the antifoaming agent used, but is usually about 0.01 to 5% by weight, preferably 0.5 to 2.5% by weight in the separating layer.
% By weight.

The indicator of the present invention has a color-changing ink layer and a non-color-changing ink layer formed on an isolation layer. In particular,
It is preferable that the color-changing ink layer and the non-color-changing ink layer are formed so as to be in direct contact with the separating layer. This allows
Elution of the ink components of the color-changed ink layer and the non-color-changed ink layer is prevented, and clear color changeability can be secured.

In the indicator of the present invention, if necessary, a plastic film layer may be formed on the color-change ink layer and / or the non-color-change ink layer. By forming a plastic film layer, more excellent water resistance can be imparted. The plastic film is not limited, and examples thereof include films of polyester, polypropylene, polyacetal, polyvinylidene chloride and the like.

The plastic film layer may be formed by laminating a plastic film formed in advance on a color-change ink layer and / or a non-color-change ink layer, or by applying a solution or dispersion containing a plastic to the color-change ink layer and / or the non-color-change ink layer. It can be formed by coating on top. 2. Method for Producing Discoloration-Aging Indicator The method for producing the indicator of the present invention is not particularly limited as long as the above configuration is obtained. For example, by applying an ink for a separating layer for forming a separating layer, a color-changing ink for forming a color-changing ink layer, and a non-color-changing ink for forming a non-color-changing ink layer to a base material, layer,
What is necessary is just to form a discoloration ink layer and a non-discoloration ink layer, respectively. In this case, if necessary, the above-mentioned plastic film layer, moisture-absorbing layer and the like can be similarly formed.

In the present invention, in particular, after forming an isolating layer on a substrate with an aqueous ink having an ink pH of 7 or more (preferably 8 to 10), a part or all of the isolating layer is formed with a color-changing ink and a non-color-changing ink. By forming a color-change ink layer and a non-color-change ink layer, respectively, the indicator of the present invention can be suitably manufactured.

As the ink for the separating layer, an aqueous ink in which components contained in the separating layer are dissolved or dispersed in water can be suitably used. This component may be the same as described above. In particular, resin components include emulsions, aqueous solutions,
Any form such as dispersion can be used. The above-mentioned additives can be contained in the aqueous ink as needed.

The content of each component in the above-mentioned aqueous ink is not particularly limited, but may be usually about 1 to 60% by weight of the resin component. When an extender pigment or the like is blended, the extender pigment may be about 1 to 50% by weight, a thickener about 0.1 to 10% by weight, and a defoamer about 0.1 to 5% by weight.

The pH of the aqueous ink is preferably 7 or more (preferably 8 to 10). By setting the pH within the above range, the discoloration can be made clearer. The above pH may be adjusted, if necessary, with a pH adjuster such as a basic substance such as sodium hydroxide, ammonia and triethanolamine, and an acidic substance such as acetic acid, phosphoric acid and hydrochloric acid.

As the color changing ink, an ink obtained by dissolving or dispersing the components contained in the color changing ink layer in an organic solvent can be suitably used. This component may be the same as described above. The additives can also be included in the discoloring ink as needed.

The type of the organic solvent is not particularly limited, and can be appropriately selected according to the type of the resin component used, the method of forming the color-change ink layer, and the like. In the present invention, since it is preferable to form the color changing ink layer by a known printing method, an organic solvent having an evaporation rate suitable for printing can be preferably used. For example, methyl alcohol, ethyl alcohol,
aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc. Glycol ethers and the like. Among them, a mixed solvent of an aliphatic alcohol and a glycol ether and a single solvent of a glycol ether are preferable in that they have an appropriate drying rate.

The content of each component in the color-change ink is not particularly limited, but is usually 50 to 2,000 parts by weight (preferably 100 parts by weight) of the organic solvent with respect to 100 parts by weight of the oil-soluble resin.
To 1000 parts by weight) and about 0.5 to 50 parts by weight (preferably 1 to 25 parts by weight) of the dye. When a fixing dye is used, the amount of the fixing dye may be 1 to 30 parts by weight (preferably 2 to 20 parts by weight) based on 100 parts by weight of the oil-soluble resin.

The non-color-change ink is not limited as long as it does not change color due to temperature and / or humidity and elapsed time. Commercially available ordinary color inks can also be used as such inks. For example, a water-based ink, an oil-based ink, a solventless ink, and the like can be used. When printing, known letterpress ink, gravure ink, depending on the printing method,
Screen ink, offset ink and the like can be properly used. These inks may be used alone or as a mixture of two or more.
In addition, the ink in the non-color-change layer may contain components (for example, a resin-based binder, an extender, and a solvent) that are mixed in a known ink.

The formation of the separation layer, the color-change ink layer, the non-color-change ink layer, etc. may be performed by a known method using each ink. For example, the printing can be performed according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, or flexographic printing. In addition, it can be formed by a roller, brush coating, spraying or the like.
Alternatively, each layer can be formed by immersing the base material in the ink. It is particularly suitable for a material into which the ink penetrates, such as paper and nonwoven fabric. In the present invention, a printing method is particularly suitable.

The thicknesses of the color-change ink layer, the non-color-change ink layer, the separating layer and the like can be appropriately set according to the kind of raw material used in each layer, the purpose of use of the indicator, and the like. Non-discoloring ink layer is 0.1-30μ
m (preferably 1-20 μm), and the isolation layer is 1-50
It may be about μm (preferably 5 to 20 μm).

In the case of forming a plastic film layer, the thickness of the plastic film layer may be appropriately determined depending on the kind of plastic used, desired water resistance and the like, but is usually about 5 to 100 μm, preferably 10 to 100 μm. 3
It may be 0 μm.

When the indicator of the present invention is placed in a specific atmosphere, the discolored ink layer discolors according to the temperature and / or humidity and the elapsed time, and more accurately by the color difference (ΔE * ab). Atmosphere state or elapsed time can be recognized.

[0044]

The indicator of the present invention has a color-changing ink layer and a non-color-changing ink layer formed particularly on the separating layer.
For this reason, the discoloration performance according to the environmental conditions (temperature and / or humidity) and the elapsed time is exhibited over a long period of about one week to two years, and the discoloration (color difference) can be accurately confirmed.

The indicator of the present invention may be, for example, a food,
It can be suitably used as an indicator for managing products such as medical products and electronic components.

[0046]

EXAMPLES Examples and comparative examples will be shown below to explain the features of the present invention in more detail. However, the scope of the present invention is not limited to these examples.

Example 1 (1) Preparation of Discoloration Ink 1 part by weight of cyanine dye (CI Basic Red 37)
Oil-soluble resin (trade name “Supra Pearl AP-30”, BA
20 parts by weight of a styrene-maleic acid copolymer manufactured by SF Co., Ltd.
0 "(manufactured by BASF) and 2.5 parts by weight of an organic solvent (ethylene glycol monoethyl ether) were mixed and stirred and dissolved at 60 ° C. for 2 hours to obtain a red ink. (2) Preparation of Ink for Separation Layer 40 parts by weight of an acrylic ester emulsion (trade name “Nicazol RX-878A”, manufactured by Nippon Carbide Industries), 50 parts by weight of water, 10 parts by weight of calcium carbonate, and an antifoaming agent (trade name) "BYK-022", manufactured by BYK-chemie)
0.5 parts by weight were mixed and stirred at room temperature for 2 hours to obtain an ink for a separating layer. The pH of this ink was 9. (3) Preparation of non-color-changing ink As a normal color ink, “26” of the Sericol EG series
Using “1 red yellow”, “791 grass” and “000 medium” (all manufactured by Teikoku Ink), the color was changed to almost the same color as the color-changed ink to obtain a non-color-changed ink. (4) Preparation of indicator Plastic film ("Peachcoat WE-135")
An ink for an isolating layer was printed on paper (manufactured by Nisshinbo) and dried to form an isolating layer. When the pH of the water in contact with the formed isolation layer was measured, pH 9 was maintained.
Next, the design “EN” shown in FIG.
"D" was subjected to silk screen printing (150 mesh) with a discoloration ink to form a discoloration ink layer. Then, the design "END (numeric character)" shown in FIG. 2 was silk-screen printed (300 mesh) with a non-color-changing ink so as not to overlap with the color-changing ink layer, thereby obtaining a red-brown indicator over the entire surface. In the present invention, either of the designs shown in FIGS. 1 and 2 may be used as the color-change ink layer or the non-color-change ink layer. In addition, the order of printing both designs may be first.

Comparative Example 1 An indicator was prepared by printing in the same manner as in Example 1 except that no isolation layer was formed.

Test Example 1 The indicators obtained in Examples and Comparative Examples were tested at a temperature of 20
The sample was placed in an environment at a temperature of 65 ° C. and a relative humidity of 65%, and the discoloration was observed.

As a result, in the indicator of Example 1, the character of "END" from reddish brown to green was clearly displayed, and the color change was confirmed. The time required for discoloration (end point) is 1
80 days. On the other hand, the indicator of the comparative example is 18
After 0 days, there was no change and no characters appeared.

[Brief description of the drawings]

FIG. 1 is a view showing a design of a color-change ink layer in an example.

FIG. 2 is a view showing a design of a non-color-change ink layer in an example.

Claims (10)

[Claims] Claims: 1. A discolorable time-lapse indicator having a discolorable ink layer and a non-discolorable ink layer that changes color according to temperature and / or humidity and elapsed time on a substrate, wherein the substrate, the discolorable ink layer and the non-discolorable ink Discoloration characterized by having a separation layer for separating the ink layer from the ink layer, and forming a color-change ink layer and a non-color-change ink layer on the separation layer so that part or all of the color-change ink layer is exposed to the outside air. Sexual age indicator. 2. A discoloration ink layer is formed on a part of the separation layer,
The color-changing time indicator according to claim 1, wherein a non-color-changing ink layer is formed on another portion of the separating layer. 3. The color-changed ink layer and the non-color-changed ink layer before the color change have substantially the same color, and a color difference appears between the color-changed ink layer and the non-color-changed ink layer only after the color-changed ink layer has changed color. 3. The color change aging indicator according to claim 1, wherein a color change ink layer and a non-color change ink layer are formed on the color change ink layer. 4. The color-change ink layer according to claim 1, which comprises 1) at least one of a methine dye and a cyanine dye and 2) an oil-soluble resin having a carboxyl group and / or a phenolic hydroxyl group. The discoloration time-lapse indicator according to 1. 5. The discolorable aging indicator according to claim 1, wherein the separating layer substantially comprises a resin component. 6. The isolation layer further comprises an extender pigment.
The described discoloration aging indicator. 7. The method according to claim 1, wherein the moisture in contact with the isolation layer is p.
The discoloration time-lapse indicator according to any one of claims 1 to 6, which is H7 or more. 8. The method according to claim 1, wherein after forming the separation layer on the base material with an aqueous ink having an ink pH of 7 or more, the color-change ink layer and the non-color-change ink layer are formed on the separation layer with the color-change ink and the non-color-change ink, respectively. Method for producing a discoloration time-lapse indicator. 9. The method according to claim 8, wherein the discoloring ink contains 1) at least one of a methine dye and a cyanine dye and 2) an oil-soluble resin having a carboxyl group and / or a phenolic hydroxyl group. 10. The production method according to claim 8, wherein the aqueous ink contains a resin component and an extender pigment.