JP2795014B2 - Indicator for storage temperature management - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a storage management indicator. More specifically, it is irreversibly colored or colored when exposed to a predetermined temperature or more, and is applied to the transportation or storage of articles requiring various temperature controls, such as frozen foods, fresh flowers, pharmaceuticals, and the like. The present invention relates to a storage temperature management indicator effective for detecting whether or not the storage temperature has been maintained.

[0002]

2. Description of the Related Art Conventionally, there are a wide variety of articles that need to be displayed, stored, transported, and the like under strict temperature control. In particular, in recent years, with the spread of cold chains, a large amount of frozen or refrigerated foodstuffs has come out, and strict temperature control is required for handling them. In other words, in such frozen or refrigerated food, during the process of transportation and storage after it is manufactured and handed over to general households, if the temperature is not controlled below the temperature specified for each food, deterioration of the contents and germs of various bacteria Corruption due to breeding may occur and become a major social problem. Such strict temperature control is required not only for frozen or refrigerated foods, but also for fresh flowers, pharmaceuticals (eg, certain anticancer drugs, vaccines, blood for transfusion), photographic drugs, chemicals, foods, magnetic materials, etc. Of various types. However, at present, it is difficult to easily know whether or not an article that requires strict temperature control typified by frozen and refrigerated foods, after production, has been subjected to the necessary temperature control and given to the user, The relevant industry calls for an appropriate indicator for temperature control.

A method for solving such a problem is disclosed in Japanese Patent Laid-Open Nos. 57-37227, 57-37228, and 59-8.
No. 4128. JP-A-57-372
In No. 27, a higher alcohol in which an oil-soluble dye is dissolved is emulsified in water. In this method, it is possible to detect whether or not the temperature is kept at a low temperature below a certain temperature, but it is possible to perform time management of the temperature history. Can not. An indicator capable of managing the time of the temperature history is disclosed in
37228 and 59-84128, all of which are suitable as indicators at relatively high temperatures near room temperature, but have the drawback that when used for management at low temperatures, they must be constantly stored at low temperatures. is there. Also, a method using microcapsules has been proposed, but a method for manufacturing the microcapsules themselves is not easy,
Further, there are problems such as storage stability, handling, and an industrial synthesis method of microcapsules that effectively work at an arbitrary temperature, and thus, they are not necessarily satisfactory indicators for storage temperature control.

[0004]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors have found that an oily substance which is liquid at room temperature and melts when the temperature exceeds the storage control temperature is converted to a nonionic surfactant and water. O / W emulsified by
When the type emulsion is frozen and then thawed, it undergoes phase separation into water and an oily substance, and only this oily substance selectively diffuses and permeates the barrier to dissolve the oil-soluble dye provided on the barrier, By diffusing and transmitting the opaque layer on the oil-soluble dye to form or color, it has been found that an abnormality in an article requiring strict temperature control can be easily detected with the naked eye, and the present invention It was completed. Since the barrier has a selectivity of diffusing and permeating only a liquid oily substance, the O / W emulsion cannot diffuse and penetrate the barrier, and does not develop or discolor unless frozen and thawed, so that the storage temperature of the indicator is wide. The function is not impaired at any angle when the indicator is stored or transported. Further, it has a feature that an emulsion used for the storage temperature management indicator can be easily prepared.

[0005]

That is, the present invention relates to an O / W type emulsion layer formed by emulsifying an oily substance which is liquid at room temperature and melts at a temperature exceeding a storage management temperature with a nonionic surfactant and water. A storage in which a barrier which selectively diffuses and transmits only the oily substance and which is provided with an oil-soluble dye on the surface opposite to the emulsion layer and an opaque layer which diffuses and transmits the oily substance are sequentially provided in a sealed container. It is a temperature management indicator. The temperature management indicator of the present invention basically has the above-described configuration, and details of the configuration are as follows.

The oily substance which is liquid at normal temperature and melts at a temperature exceeding the storage control temperature in the present invention has a melting point of about -20 to 30 ° C., for example, didecyl adipate, dimethyl adipate, acetophenone, acetochenone,
Benzyl benzoate, butyl benzoate, methyl benzoate,
Ethylene glycol, undecyl alcohol, 1-undecyl-11-ol, undecylic acid, n-octyl alcohol, oleic alcohol, oleic acid, butyl oleopalmitin oleate, caprylic acid, capric acid,
Caproic acid, lauryl caproate, diethylene glycol, cyclopentane-1,2-diol, diethylene glycol dibenzoate, diphenyl ether, dibenzyl ketone, dilinolein, dilinolenin, ethyl stearate, butyl stearate, propyl stearate, methyl stearate, stearology Olein, dimethyl suberate, diethyl suberate, monoethyl suberate, monomethyl suberate, butyl sebacate, decyl alcohol, triethylene glycol, trilaurylamine, n-nonyl alcohol, amyl palmitate,
Ethyl palmitate, octyl palmitate, decyl palmitate, dodecyl palmitate, butyl palmitate, propyl palmitate, methyl palmitate, diethyl phthalate, di-n-octyl phthalate, dimethyl phthalate, dibutyl phthalate, dilauryl phthalate , Monomethyl phthalate, t-butyl alcohol, propiophenone, 3,4-hexanediol, ethyl behenolate,
1,7-hepetane-diol, pelargonic acid, benzyl alcohol, bezophenone, pentadecyl alcohol,
Polyethylene glycol, myristyl alcohol, ethyl myristate, methyl myristate, methylhexyl ketone, glycol monolaurate, lauryl alcohol, laurylamine, ethyl laurate, dodecyl laurate, phenyl laurate, methyl laurate, linoleic acid, linoleyl alcohol , Linolenin, linoleic acid, linolenic acid, red bean oil, olive oil, apricot kernel oil, pea oil, Dutch jelly oil, oil, peanut oil,
Palm oil, pumpkin seed oil, oat oil, sesame oil, camellia oil, rapeseed oil, castor oil, jojoba oil, cottonseed oil and the like can be mentioned. The oily substance is appropriately selected according to the control temperature of the product whose storage temperature is to be controlled as described above, and one or a mixture of two or more kinds is used.

[0007] The nonionic surfactant used in the present invention is not particularly limited as long as it can keep the O / W emulsion stable.
(0 ° C.), which contributes to the destruction of the emulsion in freezing and melting, is stable in the room temperature range (for example, 10 to 30 ° C.), and contributes to the stability of the indicator in the room temperature range. .

[0008] The separation temperature (operating temperature) of the O / W emulsion in the indicator of the present invention is generally determined by the types of the oily substance and the nonionic surfactant. Therefore, the oily substance and the nonionic surfactant may be selected according to the control temperature (for example, the freezing temperature) of the product whose storage temperature is to be controlled.

In the O / W emulsion, the mixing ratio of water and the oily substance is 45/55 to 90 /
It is 10. The mixing ratio of the oily substance and the nonionic surfactant is 10/1 to 100/1 by weight.

An O / W emulsion is prepared, for example, as follows. That is, a method in which an oily substance and a nonionic surfactant which are liquid at room temperature and melt when the storage temperature exceeds the storage control temperature is gradually added to water and stirred at high speed to emulsify the emulsion, or water is added to the oily substance and the surfactant. A small emulsion can be obtained without vigorous stirring by adding a small amount of water or a small amount of water and then inverting the solubilized phase or W / O type to O / W type when the remaining amount of water is added. . Furthermore, you may process with a high pressure emulsifier.

The O / W emulsion is 15% after emulsification.
After standing still for more than an hour, only the middle trunk portion is used for the indicator except for the uppermost layer portion, which is the same as the lower layer portion of 1/20 to 1/5 and 1/10 to 1/4 volume. .

In the present invention, as a barrier for selectively diffusing and transmitting only an oily substance, a material obtained by treating paper, cloth, nonwoven fabric, or the like with a hydrophobic resin is used. Hydrophobic resin is a resin that is insoluble in water and soluble in general organic solvents, for example,
Acrylic resin, polyester resin, polyamide resin, polyurethane resin, butyral resin, polycarbonate resin, cellulose resin, petroleum resin, alicyclic saturated hydrocarbon resin, rosin resin, terpene resin, coumarone resin, epoxy resin, alkyd resin, melamine resin And phenolic resins.

As a treatment method, a method of immersing paper, cloth, nonwoven fabric or the like in a varnish obtained by dissolving a hydrophobic resin in a solvent and drying the varnish, or a method such as roll coating, gravure coating, reverse coating, or spraying the solvent solution is used. There is a method of applying to paper, cloth, non-woven fabric and the like by a usual coating method such as a coating method. The hydrophobic resin can be cross-linked with an appropriate curing agent as needed.

The barrier can control the diffusion and penetration rate of the oily substance depending on the type and thickness of the paper, cloth, nonwoven fabric, etc. used, the type of hydrophobic resin, the amount of impregnation to the base material depending on the concentration of the solution, and the crosslink density. Since the same effect is obtained even in the case of, for example, the coloring or coloring time can be managed, and a so-called coloring time management function can be provided.

The oil-soluble dyes provided on the barrier include CI Solvent Yellow 2, CI Solvent Yellow 6, and CI Solvent Yellow 6.
Solvent Yellow 14, CI Solvent Yellow 1
6, CI Solvent Yellow 21, CI Solvent Yellow 56, CI Solvent Yellow 80, CI Solvent Orange 2, CI Solvent Orange 14, CI Solvent Orange 45, CI Solvent Red 1, CI Solvent Red 3, CI Solvent Red 8, CI Solvent Red 23, CI Solvent Red 24, CI Solvent Red 25, CI Solvent Red 27, CI
Solvent Red 49, CI Solvent Red 100,
CI Solvent Red 121, CI Solvent Violet 8, CI Solvent Violet 13, CI Solvent Blue 2, CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Blue 25, CI Solvent Blue 35, CI Solvent Blue 36, CI Solvent Blue 55, CI Solvent Blue 73, CI
Solvent Green 3, CI Solvent Brown 3, C.I.
I. Solvent Brown 5, CI Solvent Black 3,
CI Solvent Black 5, CI Solvent Black 7, CI Acid Black 123, and the like.

The opaque layer may be any opaque sheet through which the oily substance can be diffused and transmitted. By providing the opaque layer, the presence or absence of coloring or coloring can be easily detected with the naked eye. As the opaque sheet, for example, paper, cloth,
A nonwoven fabric or the like can be used, and if necessary, treatment is performed with the same hydrophobic resin as that used for the barrier. The opaque layer can adjust the diffusion and penetration rate of the oily substance depending on the type and thickness of the paper, cloth, nonwoven fabric, etc. used, and when a treatment with a hydrophobic resin is performed, the base depends on the type of the resin used and the concentration of the solution. The diffusion and penetration rate can be similarly adjusted for the amount of material impregnated, the cross-linking density, and the like, so that the color development time can be controlled.

Hard glass, plastic, or the like can be used for the sealed container, but a transparent part is required to detect the presence or absence of color development with the naked eye. In order to form a sealed container, a transparent cap is attached to the opening of the main body 1 or laminated using a transparent general-purpose resin film. The dimensions of the container are not particularly limited, but usually those having an inner diameter of 0.5 to 2.0 cm and a length of 0.5 to 1 cm are used. In order to provide the storage temperature control indicator of the present invention with water resistance, the whole sealed container may be laminated with a water-resistant film. As the water-resistant film, a general-purpose resin film is used.

[0018]

The present invention will be described below in detail with reference to examples. All "parts" in the examples represent "parts by weight".

Example 1 (1) Preparation of O / W Emulsion Isopropyl palmitate (Wako Pure Chemical Industries, Ltd.) 22
5 g and Emulgen 130 (Kao Corporation) 5 g are mixed,
While stirring at about 10000 rpm with a homomixer, 275 g of water is gradually added, and O 2 is added from the solubilized phase or W / O type.
/ W type and coarse emulsification is performed. Furthermore, these are emulsified using a high-pressure emulsifier. The O / W emulsion was transferred to a separating funnel and allowed to stand for at least 15 hours, and then 100 ml of the lower layer
And take 250 ml of the middle layer and 190 ml of the upper layer
Also discard.

(2) Adjustment of selective diffusion transmission layer (barrier) of oily substance Polyester resin Byron 200 (Toyobo Co., Ltd.) 2
0 g is dissolved in 80 g of methyl ethyl ketone, and the prepared filter paper is immersed in this solution. Pull the filter paper soaked sufficiently and dry it well.

3 ml of the O / W emulsion prepared in (1) is poured into a 3 ml plastic container body, and the oily substance selective diffusion permeable layer (barrier) prepared in (2) is attached thereon. Soluble dye oil yellow # 10
1 (Orient Chemical Co., Ltd.) was scattered, a filter paper was stuck thereon, and a transparent stopper was provided to obtain a storage temperature control indicator.

When the indicator is left at -5 ° C. for 30 minutes or more and then returned to room temperature (10 ° C. to 30 ° C.), the oily substance separates and penetrates the oily substance selective diffusion transmission layer (barrier) to dissolve the oil-soluble dye. Further, the color was transmitted through an opaque layer which diffuses and transmits the oily substance, thereby clearly indicating that the substrate was placed at -5 ° C. In addition, no oily substance was separated from those stored at room temperature.

Example 2 (1) Preparation of O / W Emulsion The O / W emulsion of (1) of Example 1 was used. (2) Adjustment of oily substance selective diffusion transmission layer (barrier) The oily substance selective diffusion transmission layer (barrier) of (2) of Example 1 is used.

(3) Adjustment of Coloring Time Management Layer (Opacity Layer) Polyamide Resin Versamide 930 (Henkel White Water) 30
g) Dissolve in 70 g of isopropyl alcohol, and immerse the prepared filter paper in this solution. The filter paper fully immersed is pulled up and dried well.

3 ml of the O / W emulsion prepared in (1) is poured into a 3 ml plastic container body, the oily substance selective diffusion transmission layer (barrier) prepared in (2) is attached thereon, and then a small amount of oil Soluble dye oil yellow # 10
1 (Orient Chemical Co., Ltd.) was scattered, and a color development time management layer (opaque layer) of (3) was attached thereto, and a transparent stopper was provided to obtain a storage temperature control indicator.

When the indicator is left at -5 ° C. for 30 minutes or more and then returned to room temperature (10 ° C. to 30 ° C.), the oily substance separates and penetrates the oily substance selective diffusion transmission layer (barrier) to dissolve the oil-soluble dye. The color was then transmitted through an opaque layer which diffused and transmitted an oily substance. The time required for coloring at this time was one hour.

Example 3 (1) Preparation of O / W Emulsion The O / W emulsion of (1) of Example 1 was used. (2) Adjustment of oily substance selective diffusion transmission layer (barrier) The oily substance selective diffusion transmission layer (barrier) of (2) of Example 1 is used.

(3) Adjustment of color development time control layer (opaque layer) Polyester resin Byron 200 (Toyobo Co., Ltd.) 4
0 g is dissolved in 670 g of methyl ethyl ketone, and a filter paper prepared in advance is immersed in this solution. Pull the filter paper soaked sufficiently and dry it well.

3 ml of the O / W emulsion prepared in (1) is poured into a 3 ml plastic container main body, the oily substance selective diffusion transmission layer (barrier) prepared in (2) is attached thereon, and then a small amount of oil Soluble dye oil yellow # 10
1 (Orient Chemical Co., Ltd.) was scattered, and a color development time management layer (opaque layer) of (3) was attached thereto, and a transparent stopper was provided to obtain a storage temperature control indicator.

When the indicator is left at -5 ° C for 30 minutes or more and then returned to room temperature (10 ° C to 30 ° C), the oily substance is separated and penetrates the oily substance selective diffusion transmission layer (barrier) to dissolve the oil-soluble dye. The color was then transmitted through an opaque layer which diffused and transmitted an oily substance. The time required for coloring at this time was 5 hours.

Example 4 (1) Preparation of O / W Emulsion The O / W emulsion of (1) of Example 1 was used. (2) Adjustment of oily substance selective diffusion transmission layer (barrier) The oily substance selective diffusion transmission layer (barrier) of (2) of Example 1 is used.

(3) Adjustment of color development time control layer (opaque layer) Polyurethane resin Desmocol 500 (Sumitomo Bayer)
30 g of toluene / ethyl methyl ketone = 1/1 (w /
w) Dissolve with 70 g, and immerse the prepared filter paper in this solution. Pull the filter paper soaked sufficiently and dry it well.

3 ml of the O / W emulsion prepared in (1) is poured into a 3 ml plastic container main body, and the filter paper of the oily substance selective diffusion transmission layer (barrier) prepared in (2) is attached thereon. The oil-soluble dye oil yellow # 101 (Orient Chemical Industries) was scattered, and the color development time control layer (opaque layer) of (3) was attached thereto, and a transparent stopper was applied to obtain a storage temperature control indicator.

When the indicator is left at -5 ° C. for 30 minutes or more and then returned to room temperature (10 ° C. to 30 ° C.), the oily substance separates and penetrates the oily substance selective diffusion transmission layer (barrier) to dissolve the oil-soluble dye. The color was then transmitted through an opaque layer which diffused and transmitted an oily substance. The time required for coloring at this time was 13 hours.

Example 5 (1) Preparation of O / W Emulsion The O / W emulsion of (1) of Example 1 was used. (2) Adjustment of oily substance selective diffusion transmission layer (barrier) The oily substance selective diffusion transmission layer (barrier) of (2) of Example 1 is used.

(3) Adjustment of Coloring Time Management Layer (Opacity Layer) 20 g of polyester resin Desmophen A151 (Sumitomo Bayer) is dissolved in 80 g of methyl ethyl ketone, and Desmodur Z4370 (Sumitomo Bayer) is dissolved in this solution.
6 g is mixed with stirring, and a filter paper prepared in advance is immersed in this solution. The filter paper soaked sufficiently is pulled up and dried at 80 ° C. for 1 hour.

3 ml of the O / W emulsion prepared in (1) is poured into a 3 ml plastic container body, and the oily substance selective diffusion transmission layer (barrier) prepared in (2) is attached thereon, and then a small amount of oil Soluble dye oil yellow # 10
1 (Orient Chemical Co., Ltd.) was scattered, and a color development time management layer (opaque layer) of (3) was attached thereto, and a transparent stopper was provided to obtain a storage temperature control indicator.

When the indicator is left at -5 ° C for 30 minutes or more and then returned to room temperature (10 ° C to 30 ° C), the oily substance separates and penetrates the oily substance selective diffusion transmission layer (barrier) to dissolve the oil-soluble dye. The color was then transmitted through an opaque layer which diffused and transmitted an oily substance. The time required for coloring at this time was 21 hours.

<Evaluation Results> The storage temperature control indicators obtained in the examples were left at −5 ° C. for 30 minutes or more.
Table 1 summarizes the time required for the indicator to develop color when returned to room temperature (10 to 30 ° C).

[0040]

[Table 1]

[0041]

According to the present invention, an O / W emulsion obtained by emulsifying an oily substance which is liquid at room temperature and melts at a temperature exceeding the storage control temperature with a nonionic surfactant and water is once frozen and then thawed. In this case, phase separation occurs between water and an oily substance, the oily substance diffuses and transmits through a barrier that selectively diffuses and transmits only the oily substance, and dissolves an oil-soluble dye provided on the barrier. By diffusing and transmitting the opaque layer to form a color or color, it can be easily detected with the naked eye that there is an abnormality in an article requiring strict temperature control.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a storage temperature management indicator of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 11 ... Closed container 12 ... Main part 13 ... Transparent cap part 2 ... O / W type emulsion liquid 3 ... Barrier layer 4 ... Oil-soluble pigment 5 ... Opaque Diffusion infiltration layer 6 ... Adhesion part between main part and cap part 7 ... Adhesion part between main part and barrier layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G01K 11/06 C09K 3/00 G01K 3/02

Claims (3)

(57) [Claims] 1. An O / W emulsion layer formed by emulsifying an oily substance which is liquid at normal temperature and which melts at a temperature exceeding a storage control temperature with a nonionic surfactant and water, and selectively diffusing only the oily substance. An indicator for controlling storage temperature, wherein a barrier formed by providing an oil-soluble dye that is permeable to the surface opposite to the emulsion layer and an opaque layer that diffuses and transmits the oily substance are sequentially provided in a sealed container. 2. The storage temperature control indicator according to claim 1, wherein said barrier is paper or cloth treated with a hydrophobic resin. 3. The opaque layer which diffuses and transmits the oily substance,
3. The storage temperature management indicator according to claim 1, which is a coloring time management layer capable of variably controlling a diffusion transmission time.