JPH02290592A - Time indicator - Google Patents

Abstract

PURPOSE:To allow the distinct discrimination of an end point by holding an org. mixture composed of an electron donative colorable org. compd., a compd. contg. a phenolic hydroxyl group and an org. compd. which is liquid at ordinary temp. on a base material partially applied with inorg. powder. CONSTITUTION:A dye is not particularly limited if the dye is the electron donative colorable org. compd., for which, for example, crystal violet lactone, etc., are used. The amt. of the dye to be used is so properly determined that the part changed in the color tone intrinsic to the indicator and the part not changed therein are distinct. The org. compd. having the phenolic hydroxyl group is exemplified by monophenols to polyphenols, for which, for example, tert-butiphenol, etc., are used. The amt. thereof is usually selected from a range of about 0.1 to 50 times the electron donative colorable org. compd. 1. For example, nonyl alcohol, etc., are used as the org. which has 150 to 450 deg.C b. p. under atm. pressure and is liquid at ordinary temp. The amt. of this compd. to be used is selected to meet the effective life of the product to which the compd. is applied. The time indicator is produced by dropping this electron donative colorable org. compd. onto the base material on which characters, etc., are printed by inorg. powder, etc.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention utilizes a time indicator, more specifically, a pigment, and uses the color change to produce insect repellents, repellents, insect repellents, fragrances, antibacterial and antibacterial agents, etc. The present invention relates to a time indicator for visually determining the effective W3 period of products with limited shelf life, such as detergents, deodorants, and pharmaceuticals.

BACKGROUND ART Conventionally, various time indicators that utilize color tone changes have been proposed. They use indicators that change color tone due to chemical reactions such as neutralization reactions and redox reactions (for example, see Japanese Patent Application Laid-Open No. 60-95781).
There are also methods that utilize an indicator that causes a change in color tone upon contact with 002 gas, 02 gas, etc. in the atmosphere (see, for example, Japanese Patent Laid-Open No. 124681/1983).

<Problems to be solved by the invention> However, since all of these are greatly influenced by environmental conditions, there is a problem of reliability in correspondence with the shelf life of the product, which has the disadvantage of severely restricting its use. However, the current situation is that it is not very popular.

Recently, indicators have been proposed in which a mixture of an electron-donating color-forming organic compound, a compound having phenolic water III, and a desensitizing organic compound that is liquid at room temperature is treated as a base material. This indicator gradually becomes colored by volatilization of an organic compound that is liquid at room temperature and has a desensitizing effect.

The indicator of this method does not have a complicated mechanism and is quite effective as an indicator.

However, the drawback of this method is that it is inconvenient to select which color tone is the end point because the colors are viewed gradually.

Means for Solving the Problems> The present invention solves the disadvantage of the above-mentioned indicator, which is the ambiguity of the end point, and makes it possible to more accurately match the color change with the shelf life of the product. The above-mentioned drawbacks of the conventional techniques have been solved by providing a new indicator that is easy to store, use, etc. and economically advantageous.

That is, the present invention allows a base material partially coated with inorganic or mineral powder to hold a mixture consisting of an electron-donating color-forming organic compound, a compound having a phenolic hydroxyl group, and an organic compound that is liquid at room temperature. The area to which the powder has been applied develops color due to contact with the mixture, and due to the volatilization of the organic compound that is liquid at room temperature, the area to which the powder has not been applied changes color over time, resulting in the pattern of the area where the powder has been applied too much. The present invention relates to a time indicator characterized in that the end point is the point in time when it is no longer clearly distinguishable. Means such as dripping, impregnation, and coating are used to retain the mixture on the substrate, and application means such as spraying are used to apply the powder to the substrate.

Effect> When the time indicator of the present invention is first used, the part coated with powder is colored, and when the organic compound, which is liquid at room temperature, volatilizes over time and reaches a certain level of volatilization, The desensitizing effect of organic compounds that are liquid at room temperature weakens, and as a result, the color-developing effect of compounds with phenolic hydroxyl groups becomes stronger, and the electron-donating color-forming organic compounds begin to discolor. As the compound continues to volatilize, the coloring becomes darker, resulting in the same color as the pattern on the part where the powder is applied, and when the pattern becomes unclear at or near the end of volatilization of the liquid organic compound, the point is It will be the end point.

That is, in the time indicator of the present invention, the end point can be determined by the volatilization of the organic compound that is liquid at room temperature, and the period until the end point varies depending on the type and amount of the liquid organic compound used. Can be adjusted very easily. Therefore, the time indicator of the present invention can be applied to various products with an expiration date, and the expiration date (
(end point) can be visually determined accurately.

The dye used in the present invention is not particularly limited as long as it is an electron-donating color-forming organic compound, such as crystal violet lactone, malachite green lactone, O-damine B lactam, 2-N,N-dibenzylamino -6-
Dietylaminofluorane, 6-diethylaminobenzo[al-fluoran, 1,3-dimethyl-6-diethylaminofluorane, 3,6-bis(diethylamino)
Fluorane, γ-(4′12tro)anilinolactam,
2-(2-chloroanilino)-6-dibutylaminofluorane, 3,7-bis(dimethylamino)-10-penzoylphenothiazine, 2-7nilino-3-methyl-6
Examples include -(N-ethyl-N-7lufurylamino)fluorane.

These electron-donating color-forming organic compounds can be used alone or in combination of two or more, and can also be used in combination with other dyes.

For example, if a yellow dye and R-DCF (described later) are used together, the color starts out yellow and ends in a reddish orange color.

The amount of the above-mentioned electron-donating color-forming organic compound to be used is appropriately determined so that the original color-changed part and unchanged part of the indicator become clear, and is usually in the range of about 0.01 to 1001 Ilg per 100 cI12 of the applied substrate. It is preferable to select from

Compounds having a phenolic hydroxyl group that can be used in the indicator of the present invention include monophenols to polyphenols, as well as phenols having various substituents, such as tert-butylphenol, te
rt-amylphenol, nonylphenol, p-te
rt-octylphenol, α-naphthol, guaiacol, eugenol, 0-phenylphenol, p-phenylphenol, 4-hydroxyacetophenone, p
．． p'biphenol, bisphenol A1 bisphenol S, 4,4'-dihydroxybenzophenone, methyl p-hydroxybenzoate, methylethyl p-hydroxybenzoate, brobyl p-hydroxybenzoate, butyl p-hydroxybenzoate, 2- Ethylhexyl, 2-ethylbenzyl, 1,2-dioxynaphthalene, methylene protocatekylonate, ethyl protocatekylonate, probyl protocatekylonate, methyl gallate, ethyl gallate, brobyl gallate, p-cumylphenol , B.H.A.
, B H T , 'phenol resin, etc., but are not limited thereto.

The amount of the compound having a phenolic hydroxyl group to be used depends on the amount of the electron-donating color-forming organic compound used, but is usually 0.1 to 50% per 1 part of the electron-donating color-forming organic compound.
It is desirable to select from a range of approximately double the amount.

The boiling point is 150 at normal pressure used in the indicator of the present invention.
Typical examples of organic compounds that are liquid at room temperature of ~450°C include alcohols such as nonyl alcohol, decanol, benzyl alcohol, phenylethyl alcohol, geraniol, citronellol, hexyl cellosolve, petit norebinol, and phthalic acid. Dimethyl, diethyl phthalate, di-n-probyl phthalate, di-iso-probyl phthalate, di-n-butyl phthalate, di-is phthalate
o-butyl, diethyl adibate, di-n-adibate
Provil, di-iso-provil adibate, di-n-butyl adipate, di-iso-butyl adipate, dimethyl sebacate, diethyl sebacate, benzo'W1
n-butyl, n-amyl benzoate, n-hexyl benzoate, benzyl benzoate, iso-amyl benzoate,
Laurin I! ! n-butyl, iso-butyl laurate, lin-amyl laurate, lliso-aminolaurate, mono-n-amyl cabric acid, cabrin W1 n-hebutynoole, methyl myristate, ethyl myristate, myristic liso-proyl, linolyl brobiionate,
Esters such as geranyl acetate and tributyrin, ketones such as dibentyl ketone and petylophenone, ethers such as dihexyl ether, dibenzyl ether, and diethylene glycol di-n-butyl ether, and N-N-diethyl-m-toluamide as a nitrogen-containing compound. Examples include, but are not limited to these.

The above compounds can be used alone or in combination of two or more.

The type and amount of the organic compound that is liquid at room temperature used in the indicator of the present invention is determined by the effective lfJ of the applied product.
All you have to do is choose the appropriate one according to your time.

Furthermore, organic compounds that are liquid at room temperature include compounds that have appropriate volatility and that themselves have pest control activities such as insecticidal and repellent activities. Typical examples of such compounds include insecticides such as empenthrin and DDVP, N,N
Examples include repellents such as diethyl-m-toluamide, and anti-pep agents such as 4-chlorophenyl-31-iodobrobagyl ormal. If these are used, desired insect-proof sheets, repellent sheets, insect-killing sheets, and insect-killing sheets can be obtained which also have the indicators of the present invention.

However, in this case, the amount of the compound used cannot be too large due to safety and economic considerations, and if too little is used, color will develop quickly, so it is necessary to use a liquid at room temperature that has the same volatilization speed as the effective active compound. It is appropriate to use these organic compounds in combination.

Inorganic or mineral powders used in the indicator of the present invention include, for example, clay, silica powder, talc, acid clay, activated clay, bentonite, kaolin, celite,
Examples include diatomaceous earth, barlite, anhydrous silicic acid, hydrated silicic acid, aluminum silicate, magnesium silicate, alumina, titanium oxide, zinc oxide, etc., but are not limited to these. These may be used alone or in combination of two or more.

Furthermore, when processing the above-mentioned powder onto a substrate, cellulose-based, polyamide-based, acrylic acid, and Ester-based, vinyl acetate and copolymer-based, urethane-based, phenol-based, olefin-based, and acrylonitrile-based octamolecular compounds can be used in combination.

The indicator of the present invention is a substrate on which a mixture of the above-mentioned electron-donating color-forming organic compound, a compound having a phenolic hydroxyl group, and an organic compound that is liquid at room temperature is printed or coated with letters or patterns using inorganic or mineral powder. It is prepared by dropping, impregnating or coating on. The base material used here is not limited to a specific material, and may be the same as the various materials conventionally used for insect repellent sheets, repellent sheets, etc., such as paper, nonwoven fabric, cloth, wood, and leather. Alternatively, laminated sheets of these and other inorganic/organic fiber sheets, synthetic resins, metal sheets, etc. can be exemplified, but those that can easily absorb the above-mentioned mixture are particularly preferred.

Further, according to the present invention, these sheet substrates preferably have a color tone that allows easy visual judgment of color change, and white is particularly preferable. The obtained indicator of the present invention can be applied to a product with an expiration date by using it as it is, by cutting it arbitrarily with a knife or scissors during use, or by cutting it according to perforations made in advance to an arbitrary size.

Its applications include insect repellents, repellents, insecticides, deodorizers, air fresheners,
It can be used as a packaging material for products with expiration dates such as antibacterial and anti-bacterial agents and pharmaceuticals, and can also be applied as a tax sticker or the like to the above-mentioned products or attached to them.

Furthermore, the indicator of the present invention may contain, for example, PE. It is also possible to cover with a film such as PP or EVA.

Examples> Examples of the time indicator of the present invention are listed below.
Although explained in more detail, the present invention is not limited to this embodiment.

Example 1 Electron-donating color-forming organic compound (component A) shown in Table 1
1jl9, a compound having a phenolic hydroxyl group (component B
) 4ay, organic compound (component C) that is liquid at room temperature 100■
0.5ae of acetone solution containing 10% of inorganic or mineral powder (component D) was written on filter paper with a diameter of 71 (Toyo Shido Paper 11M grade 11G2).
The indicator of the present invention was prepared by impregnating the sample with

The obtained indicators were hung in a constant temperature room at 40° C., and changes in color tone over time were visually judged to confirm that the treated pattern could be clearly distinguished.

The results are also listed in Table 1.

The meanings of the abbreviations used in the examples are as follows: 0-DC
F 1,3-dimethyl-6-diethylaminofluorane P-DCF 3.6-bis(diethylamino)fluoran-γ-(4'-ditro)-7 nylinolactam G-DCF 2-N-N-dibenzylamino-6 −
Diethylaminofluoran R-DCF 6-diethylaminobenzo[α]-7-fluoran TH-107 2-(2-chloroanilino)-6-diethylaminofluoran CF-51 2-anilino 3-methyl-6-《N
1-Ethyl-N-7 Rufurylamino》-7 Luolan CVL 'Crystal Violet Lactone R
-L Rhodamine B lactam BMLB
Pennzoil Icomethylene Blue Resistotube RS-28
80 Gunei Chemical Industry ■ Phenol resin The abbreviations in the following examples are the same as above.

From Table 1, it can be seen that the indicators of the present invention all exhibit clear color tone changes, and as a result, the pattern portions cannot be clearly distinguished, and therefore the indicators can fully demonstrate their original functions.

Example 2 Electron-donating color-forming organic compound (component A) shown in Table 2
, a compound having phenolic water Ill group (component B), an organic compound that is liquid at room temperature (component C), 0.5 ad of an acetone solution containing MfM (#) in the parentheses (), and an inorganic or mineral powder (component D). An indicator of the present invention was prepared by uniformly impregnating a patterned φ71 filter paper (lkl2) with an acetone suspension containing 10% of the following.

The obtained indicators were hung at room temperature, and the effective period of each indicator until a change in color tone was observed and the treated pattern could no longer be clearly distinguished by visual judgment was examined. The result is the second
Also listed in the table.

From Table 2, the time indicator of the present invention can be used at a time when the pattern cannot be clearly distinguished due to a change in color tone (end point), depending on the type and amount of the organic compound that is liquid at room temperature used.
It is clear that it can be set freely.

Example 3 Diethyl phthalate 10j1ySR-DCF0.1jl9
, bisphenol AO. Acetone solution 30M containing 4■
1, write letters on the surface with a suspension containing 10% clay, adhere PE to the back side, and uniformly impregnate the surface of a filter paper (2.2 x 2 cR) treated with adhesive on the PE side to form a tack sticker. An indicator of the present invention was prepared. This product took about three months until the characters could no longer be clearly distinguished due to changes in color tone, and was useful as an indicator for the three-month period.

Example 4 A nonwoven fabric TCP-408 (Futamura Chemical) with a pattern written on it with an acetone suspension containing 10% clay was uniformly impregnated with 2 ml of an acetone solution containing di-iso-butyl adibate 1204, empenthrin 150 ms, and Resitotube PS-28803q. In this way, a time indicator of the present invention which also served as an insect repellent sheet was produced.

With this product, it took about three months for the pattern to become indistinguishable due to the change in color tone, which was in good agreement with the boldness of empenthrin.

Effects of the Invention> By combining the three components as described above, the indicator of the present invention is not affected by environmental conditions and causes a color tone change with a very simple mechanism, and this color tone change can be used for the product's shelf life. It has many features such as being able to match, being easy to manufacture, store, and use, and being obtained at extremely low cost.

Claims (3)

[Claims] (1) A base material partially coated with inorganic or mineral powder,
A mixture consisting of an electron-donating color-forming organic compound, a compound having a phenolic hydroxyl group, and a volatile organic compound that is liquid at room temperature is retained, and the part to which the powder has been applied is treated by contact with the mixture. Due to the volatilization of organic compounds that are colored and liquid at room temperature, the areas to which the powder is not applied change color over time, and the end point is when the areas to which the powder is applied can no longer be clearly identified. A time indicator. (2) An organic compound that is liquid at room temperature has a boiling point of 150 at normal pressure.
The time indicator according to claim (1), which is at a temperature of ~450°C. (3) The time indicator according to (1), wherein the boiling point of the compound having a phenolic hydroxyl group is higher than the boiling point of the liquid organic compound at room temperature.