JP2007040986A - Acidic emulsified composition for recording temperature history and indicator for recording temperature history - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsified composition for recording a temperature history, being a substance used as an indicator for recording a temperature history in order to record the history of not having frozen (non-frozen), the history of having frozen, or the history of having been unfrozen, which is demulsified in freezing and develops visible oil layer separation by being unfrozen after the demulsification. <P>SOLUTION: This emulsified composition for recording a temperature history, demulsified in freezing and developing visible oil layer separation by being unfrozen after the demulsification, contains vegetable oil and fat (excepting palm oil) containing unsaturated fatty acid and palm oil of a melting point not higher than 25°C. This emulsified composition for recording a temperature history is demulsified in freezing on condition of 10 hour storage at -20°C in cases where the composition is packed and sealed in a bag 5cm square of transparent resin film so as substantially not to leave dead space therein, and develops visible oil layer separation by being unfrozen on condition of 30 minute storage at 10°C or higher after the demulsification. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides an emulsified composition that can be de-emulsified during freezing and that can be visually distinguished by thawing after demulsification, and the temperature at which the history of non-freezing, freezing or thawing is recorded. The present invention relates to a history recording indicator, a transportation slip and temperature management body equipped with the history recording indicator, a history determination method for non-freezing, freezing or thawing of a transported article, and a physical distribution method for the article.

  In recent years, with the diversification of distribution, it has become possible to transport in various temperature ranges, and the delivery system has been enhanced and generalized, so that delivery at normal temperature, chilled and frozen temperature ranges can be selected at the individual level. It was. Although the accuracy of temperature management during transportation and storage has certainly improved due to the modernization of the distribution (distribution) system, the management of the process connecting each distribution is still not sufficient due to the complexity of small-lot delivery. In addition, it is possible to envisage a case where the finally delivered package suffers health and health damage due to inadequate temperature management on the receiving side.

  For example, when frozen foods are thawed and delivered to the home in a refrozen state, many will not notice this unless there is a significant change in physical properties. It is a danger. In addition, as an example of pharmaceuticals, fat emulsions administered intravenously break emulsion when frozen, and oil droplets associate, so that if they are injected accidentally, they will affect the lives of patients. Further, even if the change in physical properties can be remarkably visually discriminated, it cannot be determined whether the distribution (distribution) trader is deficient or the receiving side is deficient, which may cause troubles associated with delivery.

  In this way, the goods in logistics include, for example, production or processing factory stage, storage warehouse stage (room temperature, refrigerated or frozen), delivery warehouse stage, wholesale warehouse stage, retail warehouse stage, retail store display case stage, final It is placed in each of the consumer refrigerator stages and is also temporarily placed in the luggage compartment (freezer compartment, refrigeration compartment) of the transport vehicle when transporting between each stage. Therefore, there are a number of stages in the distribution of luggage, and there is a concern that the luggage is exposed to an undesirable temperature when moving the luggage from one distribution stage to another. For example, some packages may need to be refrigerated or distributed at room temperature, but they may be accidentally frozen, thawed while maintaining the frozen state, or re-frozen after the first freeze or thaw. There are times when it falls. In particular, when carrying a load on a refrigerated truck, it may take about 10 to 20 minutes at the time of loading and unloading the load, so that the load that is to be kept frozen may be thawed. For this reason, when delivering frozen baggage via the home delivery route, it is usually considered that the baggage is frozen at -20 ° C. 5 minutes, and 3 minutes in an environment of 20 ° C. is required, but it is the present situation that it is not understood what temperature history it has by looking at the packed package .

Then, when the history of non-freezing, freezing, or thawing was recorded and the possibility of the temperature history recording indicator which can distinguish the recorded contents visually was examined, the following patent documents 1-4 were discovered. That is, as a display device that displays whether or not temperature control is possible by irreversible change, Patent Document 1 discloses a technique in which brine is processed into a specific shape and sealed in a transparent container, and Patent Document 2 is microencapsulated. Techniques using various dyes are disclosed. However, the techniques disclosed in Patent Documents 1 and 2 require very advanced techniques and are expensive, so that it is difficult to make them versatile. Reference 3 discloses a thawing detector for frozen foods using an emulsion, but details of the emulsion are not described, and a temperature suitable for discriminating flaws in temperature management of goods in logistics. There is no mention of time conditions and emulsion composition. In Patent Document 4, when the creamy composition obtained by mixing at -12 ° C is heated to -2 ° C and then kept at -10 ° C, the creamy composition becomes a solid in the water layer and a solid in the oily layer. However, since this cream-like composition is obtained by cooling to -12 ° C, it cannot be used at room temperature, greatly restricting the use and storage mode. Because it receives, it is hard to say that it is practical.
Japanese Patent Publication No. 50-39583 Japanese Patent Publication No. 50-39584 Japanese Patent Laid-Open No. 52-2087 Japanese Patent Publication No. 2-31809

  An object of the present invention is an emulsified composition for use in a temperature history recording indicator for recording a history of non-freezing (non-freezing), history of freezing, or history of thawing, A temperature history recording emulsion composition and an indicator for recording the temperature history are provided, in which demulsification occurs within a predetermined time at the time, and thawing occurs after the demulsification within a predetermined time to produce a visible oil layer separation. It is to be. It is another object of the present invention to provide a transportation slip and a temperature management body equipped with the temperature history recording indicator, a method for determining a history of non-freezing, freezing or thawing of a package, and a logistics method for the package.

  In order to achieve the above-mentioned object, the present inventors have intensively studied the composition of the emulsion and the conditions for demulsification, and as a result, have examined each condition such as the composition of fats and oils, pH, acidity, salt concentration, viscosity, etc. Among them, the most important condition was that palm oil having a melting point of 25 ° C. or lower was used, and the present invention was completed.

  That is, the present invention relates to an emulsion composition for temperature history recording that generates demulsification upon freezing and causes oil layer separation that can be visually recognized by thawing after demulsification. And an emulsified composition for temperature history recording containing palm oil having a melting point of 25 ° C. or less.

  The present invention also provides a temperature history recording indicator in which the above-described emulsion composition for temperature history recording is enclosed in a content-visible container, and a transport slip or temperature equipped with the temperature history recording indicator. Provide management body.

  Furthermore, the present invention provides a history of non-freezing, freezing or thawing of a transported article to which the transportation slip is attached depending on whether or not the above-mentioned temperature history recording indicator is attached to a transportation slip and the oil layer separation of the indicator is present. Provide a method to determine

  In addition, the present invention is for temperature history recording which is carried in a predetermined logistic stage after the above-mentioned transportation slip is attached to an article, and which is enclosed in a temperature history recording indicator attached to the transportation slip. Provided is an article distribution method for determining whether oil layer separation has occurred in an emulsified composition.

  The emulsified composition for temperature history recording of the present invention causes demulsification within a predetermined time during freezing, and thawing occurs within a predetermined time after demulsification, whereby visible oil layer separation occurs. Therefore, the emulsified composition for temperature history recording can be used as a temperature history recording indicator for recording a history of non-freezing, freezing, or thawing by enclosing the emulsion in a content-visible container.

  The present invention will be described below. In the present invention, “%” means “mass%”.

  The emulsified composition for temperature history recording of the present invention is an emulsion composition for temperature history recording that causes demulsification upon freezing and causes oil layer separation that can be visually recognized by thawing after demulsification. Containing vegetable oils and fats (excluding palm oil) and palm oil having a melting point of 25 ° C. or lower.

  In the present invention, “when freezing” does not mean that the emulsified composition for temperature history recording is simply frozen, but means that it is frozen so that demulsification occurs. That is, the emulsified state of the emulsified composition for temperature history recording at room temperature exhibits a cream shape in which oil-in-water type oil layer separation is not recognized. Once this is stored in a frozen state, it freezes, the aqueous phase and the oil droplets freeze, and the constituent components grow into crystals (for example, needle crystals). It breaks emulsified micelles and causes demulsification. Accordingly, a certain amount of time is required for crystal growth and destruction of micelles. In order to cause such demulsification, freezing in a certain time width is expressed as “when freezing”. In addition, even if it becomes the state of demulsification by freezing, since it is in a frozen state at this time, fats and oils separation does not arise and it cannot visually discriminate | determine. Next, when it is thawed or melted at room temperature or a chilled temperature range, oil layer separation occurs and visual discrimination becomes possible. Further, even when complete oil layer separation does not occur, if fine oil layer separation occurs, the cream changes color and can be visually discriminated.

  FIG. 1 shows a state before freezing of the emulsified composition for temperature history recording, that is, a state where fine oil droplets are emulsified in the aqueous phase. When this emulsified composition for temperature history recording is frozen at −20 ° C. for 7 hours, the outline of the oil droplet becomes blurred as shown in FIG. When this state (the state of being frozen) is observed macroscopically, it appears that there is no change from the state before freezing. However, demulsification has already occurred, and the state is only forcibly fixed by freezing. Therefore, when the emulsified composition for temperature history recording of FIG. 2 starts to be thawed, the oil droplets start to aggregate as shown in FIG. 3, and the oil phase becomes larger as shown in FIG. This means that “a visible oil layer separation is generated by thawing after demulsification”. The term “thawing” means placing the frozen emulsion for temperature history recording in a temperature atmosphere of, for example, 5 ° C., 10 ° C., and 20 ° C. At that time, the vegetable oil and fat containing coagulated or crystallized palm oil is usually melted and liquefied. This liquefaction causes oil layer separation. 1 to 4, the scale width at the lower right corner of each figure indicates a length of 10 μm.

  The emulsified composition for temperature history recording of the present invention has the characteristics described above, and as a configuration for realizing such characteristics, vegetable oils and fats (unless palm oil) containing unsaturated fatty acids and palm oil are used. Is used.

  In the present invention, vegetable fats and oils (excluding palm oil) containing unsaturated fatty acids are refined fats and oils containing unsaturated fatty acids of linoleic acid and linolenic acid in triglycerides of vegetable fats and oils, such as rapeseed oil, soybean oil, corn Oil, safflower oil, sunflower oil, and the like. Among these, rapeseed oil is preferred when used in the −20 ° C. range, which is a general refrigeration condition, from the viewpoint that oil layer separation can be clearly distinguished. Furthermore, soybean oil is preferred when used in the low temperature range of -30 ° C. In addition, since the time required for demulsification will become long when there are too few ratios of the unsaturated fatty acid in vegetable fats and oils except palm oil, it is preferably at least 80 mass% or more.

  In this invention, palm oil means what refine | purified the oil obtained from the palm palm. In particular, in the present invention, the melting point of palm oil is 25 ° C. or lower, preferably 18 ° C. or lower, more preferably 12 ° C. or lower. The reason for this is that when palm oil having a melting point of more than 25 ° C. is used, a good emulsified state cannot be obtained, which is inconvenient for actual use as a temperature history recording indicator. In addition, 2 or more types of palm oil from which melting | fusing point differs can also be mixed and used as palm oil.

  In the emulsified composition for temperature history recording of the present invention, the total fat content of the aforementioned vegetable oil and palm oil is less likely to cause demulsification, and the oil layer is separated even under inappropriate distribution and storage conditions. May not achieve the purpose of recording the temperature history. If too much, demulsification tends to occur, and oil layer separation occurs even if the degree of deviation from proper distribution and storage conditions is slight. However, it may not be suitable as a practical temperature history recording material, and is preferably 40 to 80% by mass, more preferably 60 to 70% by mass.

  Moreover, 2 / 1-50 / 1 are preferable and, as for the mass ratio of vegetable oil and palm oil, 3 / 1-6 / 1 are further more preferable. When it deviates from this ratio, it may take time for freezing, and even when placed in a frozen state, demulsification tends not to occur. When the acidic emulsified composition of the present invention is filled with 5 g of a 5 cm square resin film bag so as not to substantially contain a head space, and sealed and stored at −20 ° C., the ratio of vegetable oil and palm oil is 2 / In the case of 1-50 / 1, it freezes within 10 hours, demulsification occurs, does not melt at 10 ° C. for 5 minutes, but melts within 20 minutes, and does not melt at 20 ° C. for 3 minutes, but 10 minutes Within thaw. Moreover, when the ratio of vegetable oil and palm oil is 3/1 to 6/1, it freezes in about 5 to 6 hours, demulsification occurs, and it does not melt at 10 ° C. for 3 minutes, but it melts within 10 minutes. However, it does not melt at 20 ° C. for 2 minutes, but melts within 5 minutes.

  A colorant can also be added to the emulsion composition for temperature history recording of the present invention so that the oil layer separation can be visually confirmed clearly when the oil layer separation occurs after demulsification. For example, oil layer separation can be visually clarified by adding, for example, β-carotene that exhibits a yellow color.

  The pH of the emulsion composition for temperature history recording of the present invention is preferably 5 or less, more preferably 4 or less. If the pH is higher than this, it is microbially unstable and is not suitable for room temperature storage. To store at room temperature, it is necessary to sterilize at high temperature and high pressure or add a strong preservative, which adversely affects the emulsified state. Because it gives. Further, in order to impart microbial stability, it is preferable to add sodium chloride to the emulsion composition for temperature history recording of the present invention. However, if the pH is too low or the salt concentration is too high, the emulsified state tends to be adversely affected. The acidity is preferably 0.5 to 1% by mass in terms of acetic acid. The salt concentration is preferably adjusted to 1.5 to 4% by mass.

  The emulsified composition for temperature history recording of the present invention usually contains 10 to 40% by mass of water in order to maintain the emulsified state. As water, tap water, distilled water, or ion exchange water can be used. In addition, you may contain water miscible organic solvents, such as ethanol and glycerol, in the range which does not impair the effect of this invention.

  In the emulsified composition for temperature history recording of the present invention, a pH stabilizer can be used in order to suppress the pH variation with time. Examples of pH stabilizers include citrate and phosphate. In particular, by using what is prescribed for food additives such as Na glutamate, and using only other ingredients that are permitted as foods, it is possible to ensure health even if they are consumed.

  Since the emulsion composition for temperature history recording of the present invention is an emulsion composition containing fats and oils, it can contain a composition having an emulsifying function such as an emulsifier. Examples of the emulsifier include sorbitan fatty acid ester and glycerin fatty acid ester, but food additives such as sucrose fatty acid ester and lecithin can be used for the same reason as described above. Moreover, protein foods, such as egg yolk of birds, such as a chicken egg, protein, milk protein, and soy protein, can also be used. Egg yolk having a large emulsifying action is particularly preferable. However, if the amount of egg yolk is too large, the oil layer separation may become visually unclear, and it is preferable that the amount added does not exceed 5% by mass.

  If the viscosity of the emulsified composition for temperature history recording of the present invention is too low, it is difficult to keep the emulsified state stable, the handling property is lowered, and if too high, handling such as preparation and filling of the emulsified composition is difficult. Since it becomes difficult, it is preferably 70 to 400 Pa · s, more preferably 150 to 250 Pa · s.

  In order to prepare a cream having such a viscosity range, the emulsion composition for temperature history recording of the present invention includes starch, modified starch, wet heat-treated starch, saccharides such as dextrin and sugar alcohol, hemicellulose and pulp. Etc., egg whites such as chicken eggs that are protein food materials, and the like can be added. In particular, egg white is preferable because it can give a body feeling to the emulsified composition with a small amount of addition, compared to the saccharides and dietary fibers. It is preferable that the amount used does not exceed 5% by mass. This is because preparation and handling become difficult if too much. In addition, as egg white, dried egg white can be rehydrated and used.

  Furthermore, a thickening stabilizer can be added to the emulsified composition for temperature history recording of the present invention in order to stabilize the emulsified state. Examples of the thickening stabilizer include polymer compounds such as CMC-Na. Examples of food additives include xanthan gum, tamarind gum, guar gum, locust bean gum, crystalline cellulose, and the like, among which xanthan gum is preferable in terms of emulsion stability. In this case, if the blending amount is too small, it is difficult to keep the emulsified state stable, the handling property is lowered, and if it is too large, handling such as preparation and filling of the emulsified composition becomes difficult, so preferably 0. 0.001 to 0.1% by mass.

  The emulsified composition for temperature history recording of the present invention can be produced as described below.

  First, clean water to be used, emulsifier or egg yolk, and if further used, a pH adjuster (acidulant, acetic acid, brewed vinegar, etc.), salt, pH stabilizer, emulsion stabilizer, sugar or egg white, etc. are mixed together, Hobart mixer Etc. to prepare a uniform mixed solution. While stirring the resulting mixed solution, a small amount of fat and oil obtained by mixing unsaturated vegetable oil and palm oil is added to this mixed solution while confirming that it is emulsified. When the fat and oil are added, stirring is continued until the fat and oil are not separated to obtain a crude emulsion. In this case, vegetable oils and fats containing unsaturated fatty acids (excluding palm oil) and palm oil having a melting point of 25 ° C. or lower in a ratio of 2/1 to 50/1 so that the sum is 40 to 80% of the total mass. It is preferable to mix and emulsify. Furthermore, it mix | blends the vegetable oil and fat and palm oil containing an unsaturated fatty acid in the ratio of 3 / 1-6 / 1 so that the sum total may be 60-70% of the total mass, and the acidity of acetic acid conversion is 0.5- It is more preferable to prepare and emulsify 1% by mass and a salt concentration of 1.5 to 4% by mass.

  Next, the obtained crude emulsion is transferred to a high-speed mixer and stirred at a high speed to minimize the particle shape of the emulsion, thereby obtaining a stable emulsion composition for temperature history recording. Furthermore, it is preferable to deaerate the emulsified composition for temperature history recording by transferring this to a deaerator with a stirring function and stirring in a vacuum state.

  The emulsified composition for temperature history recording of the present invention always exhibits a cream form in which oil layer separation is not observed when stored in a room temperature range. Once this freezes, it will be in a demulsified state. Even after demulsification, the separation of fats and oils that can be visually recognized if it remains frozen does not occur. Next, when this is placed in a room temperature or chilled temperature zone and thawing or melting, oil layer separation appears irreversibly, and the separated oil layer can be visually recognized. Even when complete oil layer separation does not occur, if fine oil layer separation occurs, the cream changes color and is visible. By utilizing such a phenomenon, the temperature history of the emulsion composition for temperature history recording can be grasped as described below.

  When the oil layer separation cannot be confirmed in the temperature history recording emulsion composition at room temperature, it indicates that the temperature history recording emulsion composition has not yet been frozen. Similarly, when the oil layer separation can be confirmed in the temperature history recording emulsion composition in the normal temperature range, the temperature history recording emulsion composition is once stored in the freezing temperature zone, frozen, and demulsified. It shows that it thawed.

  In addition, when oil layer separation cannot be confirmed in the temperature history recording emulsion composition in the freezing temperature zone, it indicates that the temperature history recording emulsion composition has never been thawed while frozen. . Similarly, when oil layer separation can be confirmed in the temperature history recording emulsion composition in the freezing temperature zone, oil layer separation occurs irreversibly, so this temperature history recording emulsion composition was once stored in the freezing temperature temperature zone. It has been shown to have been frozen and demulsified, then thawed and re-frozen.

  The demulsification rate during freezing and the oil layer separation rate during thawing of the emulsion composition for temperature history recording of the present invention is a rate according to the intended use of the emulsion composition for temperature history recording. Is desired. For example, it is necessary to freeze and demulsify in as short a time as possible in order to record that a normal temperature distribution / preserved product that does not need to be frozen has been frozen. If demulsification takes too long, oil layer separation does not occur and the temperature history is recorded when the emulsified composition for temperature history recording thaws, despite the fact that the normal temperature distribution / preserved product has been frozen and denatured. This is because no freezing denaturation can be confirmed.

  In addition, in order to properly record the history of thawing of a frozen product, it is necessary that the emulsion composition for temperature history recording is thawed (melted) under appropriate temperature conditions and time so that oil layer separation occurs. is there. If the time until the thawing of the emulsion composition for temperature history recording is too long, when the frozen product is once thawed and re-frozen, the temperature history recording emulsion composition does not cause oil layer separation and the temperature history is recorded. It will not be done and you will not be able to confirm thawing. On the other hand, if the melting time of the temperature history recording emulsion composition is too short, the emulsion for temperature history recording can be used in an extremely short time that does not affect the frozen product, even in the process of being placed in a room temperature or chilled temperature zone as required. This is because the composition exhibits oil layer separation and a frozen product having no problem is erroneously determined to have been thawed.

  Therefore, the emulsified composition for temperature history recording of the product of the present invention contains 5 g of a 5 cm square resin film (for example, nylon (15 μm thickness) / polyethylene (50 μm thickness)) so that it does not substantially contain headspace. When filled and sealed at -20 ° C, if the ratio of vegetable oil and palm oil is 2/1 to 50/1, it freezes within 10 hours, demulsification occurs, and 5 minutes at 10 ° C Does not melt, but melts within 20 minutes, does not melt at 20 ° C. for 3 minutes, but melts within 10 minutes. Moreover, when the ratio of vegetable oil and palm oil is 3/1 to 6/1, it freezes in about 5 to 6 hours, demulsification occurs, and does not melt at 10 ° C. for 3 minutes, but melts within 10 minutes. However, it does not melt at 20 ° C. for 2 minutes, but melts within 5 minutes. Further, it does not melt at 5 ° C. for 30 minutes, preferably 1 hour.

  The emulsion composition for temperature history recording of the present invention described above can visually confirm the contents depending on the use, and the contents of a plastic film bag, plastic container, etc. that are entirely or partially transparent or translucent. By filling the object-visible container with a full amount so that it does not substantially contain air and sealing it, it can be preferably used as a temperature history recording indicator for recording a temperature history of non-freezing, freezing or thawing. An example of such a content-visible container is a flat bag made of a resin film, in which at least a part of the resin film is transparent so that the content can be visually recognized.

  The type and capacity of the container used for the temperature history recording indicator can be selected according to the application. However, all or part of the container needs to be transparent or translucent. This is because the oil layer separation is visually discriminated. Although the material of the container is not particularly defined, a material having refrigeration resistance is preferable in consideration of being placed in a frozen state. Moreover, what has the intensity | strength of a grade which is not damaged when an emulsion-like composition freezes is preferable. Furthermore, it is preferable that the material has an appropriate gas barrier property in consideration of oxidation of the contents and evaporation of water vapor. For example, a resin film made of nylon (Ny) / polyethylene (PE) or a silica-deposited laminate material can be used. For the above reasons, polyethylene terephthalate (PET) vapor-deposited laminate films (PET / Ny / PE) are preferred. Specific examples of other preferable resin films include a resin film having a two-layer structure of Ny (usually 5 to 40 μm thickness) / PE (heat seal layer (usually 20 to 100 μm thickness)) and PET (usually 5 to 40 μm thickness). Examples thereof include a resin film having a three-layer structure of / Ny (usually 5 to 40 μm thickness) / PE (usually 20 to 100 μm thickness).

  The form and type of the container used for the temperature history recording indicator are not particularly defined, and examples thereof include a bag-like container bonded with a film, a flexible plastic container, or a molded container such as glass or hard plastic. In addition, the size of the indicator is not particularly defined, but in order to satisfy the condition of being visually discernable, the mass of the emulsified composition as the temperature history recording material of the indicator is 0.3 g or more. Is preferably 0.5 g or more. For example, when the target for determining the temperature history is delivered to the home, that is, within a mass of about 30 kg, the mass of the emulsified composition as the temperature history recording material of the indicator may be 0.5 to 1 g, which is even larger. When it is the target product, the mass of the emulsified composition can be increased. It is also possible to install a plurality of indicators with similar masses at different locations.

  FIG. 5 shows another aspect of the temperature history recording indicator. The indicator 50 is sealed around the two transparent resin films, and a flat bag 52 in which the emulsified composition 51 for temperature history recording is enclosed as a content, and a surface protection disposed so as to sandwich the flat bag 52. As shown in FIG. 6, an adhesive (not shown) having a member 53 and a back surface protection member 54 is disposed on the peripheral portions of the surface protection member 53 and the back surface protection member 54 facing each other. It has an integrated structure. Here, the surface protection member 53 is provided with an opening 55 that allows the flat bag 52 to be observed from the outside. Accordingly, the temperature history of the temperature history recording indicator 50 can be known from the opening 55 by observing the temperature history recording emulsion composition contained in the flat bag 52. There is no restriction | limiting in particular in the shape of an opening part.

  Further, the front surface protection member 53 and the back surface protection member 54 can be formed from Kent paper, paperboard, plastic sheet, or the like, respectively. When a heat-sealable plastic sheet is used as the plastic sheet, a structure as shown in FIG. 6 can be formed by heat sealing without using an adhesive.

  Further, a color or pattern that improves the visibility of oil layer separation caused by thawing after the emulsion composition for temperature history recording has been demulsified is printed on the surface of the back protective member 54 on the flat bag 52 side. Is preferred. The coloring is preferably performed in a color that can be clearly distinguished from the emulsified composition for temperature history recording and the original color. For example, when the color of the emulsified composition for temperature history recording is white to light yellow, it is preferably colored red also for the purpose of calling attention. In addition, characters such as a checkerboard pattern and “bad” can be printed. You may combine a coloring part and a pattern. In addition, the coloring or pattern printing area may be provided on the entire surface of the back surface protection member 54 on the flat bag 52 side, or may be provided only on at least a part of the area corresponding to the opening 55. Thus, when the visibility of oil layer separation is improved, such as coloring or a pattern being printed on the flat bag 52 side surface of the back surface protection member 54, the surface protection member 53 may be omitted.

  Further, as yet another aspect of the temperature history recording indicator, in the configuration corresponding to the flat bag 52 of FIG. 5 without using the front surface protection member 53 and the back surface protection member 54, the one side of the flat bag contains the contents. It is transparent so that it can be visually recognized, and is colored and / or patterned so as to improve the visibility of oil layer separation caused by thawing after the emulsion composition for temperature history recording has been demulsified. Can be mentioned. In this case, the resin film constituting the flat bag is directly printed, but it is preferable that the printing does not directly contact the emulsion composition for temperature history recording. For example, when a resin film having a two-layer structure of nylon / polyethylene is used as the resin film, printing can be performed on either side of nylon, but printing can be performed on the nylon surface on the polyethylene side in consideration of printing scratch resistance. preferable. In addition, when a film having a three-layer structure of polyethylene terephthalate / nylon / polyethylene is used, printing can be performed on any surface of nylon or any surface of polyethylene terephthalate, but when printing on the outermost layer of polyethylene terephthalate, It is preferable to perform printing excellent in scratch resistance.

  In these temperature history recording indicators, when the oil layer separation cannot be confirmed in the emulsified composition for temperature history recording enclosed in the temperature history recording indicator in the normal temperature range, the temperature history recording indicator is still frozen. It shows that there is a history of not having done it. Similarly, in the normal temperature range, when the oil layer separation can be confirmed in the temperature history recording emulsion contained in the temperature history recording indicator, the temperature history recording indicator was once stored in the freezing temperature zone and frozen. It shows that there is a history of demulsification and subsequent defrosting.

  In addition, in the freezing temperature zone, when oil layer separation cannot be confirmed in the temperature history recording emulsified composition enclosed in the temperature history recording indicator, the temperature history recording indicator may have been frozen and thawed once. This indicates that there is no history. Similarly, when the oil layer separation can be confirmed in the emulsified composition for temperature history recording enclosed in the temperature history recording indicator in the freezing temperature zone, the oil layer separation occurs irreversibly. It is shown that there is a history that it was once stored in a freezing temperature zone, frozen and demulsified, then thawed and re-frozen.

  By attaching the temperature history recording indicator of the present invention having the above-described effect to the transportation slip, the temperature history of the transported baggage can be determined based on the presence or absence of the oil layer separation of the indicator. Therefore, this aspect is useful as a method for determining the history of non-freezing, freezing, or thawing of a package with a transportation slip.

  A transport slip is a slip that is attached to a transported article (delivery product) so that a trader who transports the article manages the destination and sender's name, and therefore the transported article is delivered to the destination. In the process, that is, while being transported and stored, it is placed on the article to be transported. For example, a small package delivery slip or a tag of a post office or a courier can be cited. Further, the size, shape and type of the indicator to be mounted are not particularly defined. However, due to the nature of the transportation slip, it is preferable that the size and thickness are suitable for the size of the slip. If it is mounted on a general-purpose slip, the upper limit is 4 cm square, or the diameter is preferably 5 mm or less. Furthermore, the upper limit is 2 cm square or diameter, and a thickness of 3 mm or less is preferable in actual use. In view of visual ease, the lower limit is preferably 3 mm square, or the diameter and thickness are 2 mm or more.

  In addition, about the material of the indicator with which the transport slip of this invention is mounted | worn, the intensity | strength of the grade which does not break on the way is requested | required in consideration of being affixed and transported to a to-be-transported article. Accordingly, a molded container such as a bag-like container, a flexible plastic container, or a rigid plastic laminated with a film, which has a resistance to refrigeration and a strength that does not cause damage in handling is preferable. The use scene of general glass is limited in terms of strength.

  The temperature history recording indicator of the present invention can be used as a temperature management body in addition to being mounted on the transportation slip as described above. The temperature management body is a label, a tag, or the like with temperature management information such as temperature management conditions and handling precautions, and is attached to the article and distributed along with the article. For example, “freezing” or “freezing temperature −20” Temperature management information such as “° C.” is attached to the surface. About the magnitude | size and shape of the indicator with which it mounts, it is the same as that of the case of the above-mentioned transportation slip. Therefore, if a temperature management body equipped with the temperature history recording indicator of the present invention is attached to the management object, the temperature history of the management object can be managed.

  The transportation slip or temperature management body equipped with the temperature history recording indicator described above determines whether or not the article has been frozen, remains frozen, or has a thawed history. The present invention can be preferably applied to an article distribution method. That is, after such a transport slip or temperature management body is mounted on an article, the article is distributed and enclosed in a temperature history recording indicator attached to the transport slip or temperature management body at a predetermined distribution stage. If it is determined whether or not oil layer separation has occurred in the emulsion composition for temperature history recording, it is determined whether or not the article has a history of freezing, remains frozen, or has a thawed history. can do.

  Next, the present invention will be described in more detail based on examples and test examples. The present invention is not limited to these. In addition, about the viscosity of the emulsified composition for temperature history recording, using a B-type viscometer (Tokyo Keiki Co., Ltd.), No. The measurement was performed under the conditions of 6 rotors and 2 rpm.

Example 1
An emulsified composition for temperature history recording was prepared as described below with the formulation shown in Table 1.

  First, fresh water was put into a mixer (Kitchen Aid Co., Hobart mixer), and raw materials other than rapeseed oil and palm oil were sequentially added while stirring and stirred at high speed until evenly dissolved (stirring time: 2 minutes). When completely dissolved, rapeseed oil and palm oil were slowly added while continuing stirring to prepare a creamy crude emulsion. At this time, the temperature of the palm oil was set to the melting point or higher and was made liquid.

  Next, this crude emulsion was transferred to a high-speed mixer (manufactured by Sanyo Electric Co., Ltd., home mixer) and stirred to perform fine emulsification (stirring time: 1 minute). The obtained emulsion was put into a deaeration kettle with a stirring function and stirred while taking a vacuum. When the degree of vacuum of about 0.09 MPa was obtained, the vacuum was gradually released, and the emulsion was taken out of the deaeration kettle when it returned to normal pressure to obtain the emulsion composition for temperature history recording of the present invention. The emulsion composition for temperature history recording has a light egg color and is a smooth cream emulsion. As a result of analysis, pH 4.0, acidity 0.7% by mass in acetic acid, salt concentration 2% by mass, The viscosity was 220 Pa · s.

Example 2
An emulsified composition for temperature history recording was prepared in the same manner as in Example 1 with the formulation shown in Table 2. The obtained emulsion composition for temperature history recording was light yellow and was a smooth cream emulsion. As a result of analysis, pH 3.8, acetic acid equivalent acidity 0.8 mass%, salt concentration 2 mass% The viscosity was 180 Pa · s.

Example 3
An emulsified composition for temperature history recording was prepared in the same manner as in Example 1 with the formulation shown in Table 3. The obtained emulsion composition for temperature history recording had a pale yellow color and was a smooth cream emulsion. As a result of analysis, pH 4.1, acidity 0.7% by mass in terms of acetic acid, and salt concentration 3% by mass were obtained. The viscosity was 280 Pa · s.

Example 4
An emulsified composition for temperature history recording was prepared in the same manner as in Example 1 with the formulation shown in Table 4. However, the total HLB of the emulsifier was adjusted to be 11. The obtained emulsion composition for temperature history recording had a pale yellow color and was a smooth cream emulsion. As a result of analysis, it was found to have a pH of 3.6, a salt concentration of 3% by mass, and a viscosity of 250 Pa · s.

Example 5
An emulsified composition for temperature history recording was prepared in the same manner as in Example 1 with the formulation shown in Table 5. The obtained emulsion composition for temperature history recording was white and was a smooth cream emulsion. As a result of analysis, it was pH 3.6, a salt concentration of 3% by mass, and a viscosity of 100 Pa · s.

Test example 1
5 g of the emulsified composition for temperature history recording obtained in Example 1 is filled into a bag (5 cm square) made of a laminate film of nylon (15 μm thick) and polyethylene (50 μm thick), and hermetically sealed so as not to contain air. did. When this was stored frozen at −20 ° C., it was frozen in 4 hours. Then, as a result of storing this at 20 ° C., it was thawed in 5 minutes, oil layer separation was developed, and it was confirmed visually and clearly.

Test example 2
The compounding quantity of the rapeseed oil and palm oil of Example 1 was changed as shown in Table 6, and the test was conducted according to Test Example 1. Table 6 shows the time required for freezing.

  From Table 6, as a result of changing the blending ratio of rapeseed oil and palm oil (rapeseed oil / palm oil) in the blending of Example 1, any blending is in a frozen state within 10 hours allowed as a temperature history recording material. I was able to confirm. In particular, it was confirmed that the blending ratio was 2 to 50 within 6 hours, and the blending ratios 3 to 6 were frozen within 4 hours.

Example 6
An acidic emulsified form as a temperature history recording material obtained in Example 1 on a transparent resin sheet (PET) formed so as to have a cylindrical depression having a diameter of 10 mm and a depth of 5 mm at the center of a 2 cm square sheet. About 0.4 g of the composition was filled, heat sealed with an aluminum sheet, and sealed to obtain a temperature history recording indicator.

  The obtained temperature history recording indicator was affixed to the surface of a frozen food box containing paper, and this frozen food was stored at -20 ° C for 5 hours, then stored at 20 ° C at room temperature for 60 minutes, and again at -20 ° C for 10 hours. saved. Frozen foods are in a frozen state and remain unchanged in appearance, but the emulsified composition as a temperature history recording material enclosed in the indicator is separated from the oil layer, and it can be visually determined that it has been thawed once. It was.

Example 7
About 1 g of the emulsified composition for temperature history recording obtained in Example 1 was filled in a transparent resin bag in which two 2 cm square PET vapor-deposited laminated film sheets were stacked and sealed in three directions, and the head space was made as much as possible. An indicator for temperature history recording was obtained by hermetically sealing in the lost state.

  The obtained temperature history recording indicator was affixed to the surface of the outer box of the fat emulsion, and this fat emulsion was stored at −30 ° C. for 10 hours, frozen, and thawed at room temperature of 25 ° C. for 24 hours. When the indicator attached to the outer box was observed, the emulsified composition as a temperature history recording material showed no noticeable oil layer separation, but the color tone changed, and it was visually confirmed that it was frozen and thawed once. I was able to distinguish it. In addition, when the fat emulsion was visually observed, it was indistinguishable from the normal product in appearance, but when observed with a microscope, the particle size of the micelles was enlarged by freezing denaturation, and was usually 0.3 μm or less, several μm. Many things were recognized. This state has a risk of occluding fine blood vessels when injected into the human body, and is not suitable as a fat emulsion.

Example 8
The temperature history recording indicator obtained in Examples 6 and 7 is attached to a transportation slip used for courier service, and affixed to the top or side surface of each package for transportation at room temperature, chilled transportation, and frozen transportation. When pasted, the indicator was attached to the package during the process of delivering the package to the destination, and the temperature history could be confirmed during both the transportation and storage. Accordingly, the temperature-history recording indicator-equipped transportation slip fulfilled the function as an indicator without being damaged in any of the temperature zones of normal temperature transportation, chilled transportation, and freezing transportation.

Example 9
5 g of the emulsified composition for temperature history recording obtained in Example 1 is filled into a bag (5 cm square) made of a laminate film of nylon (15 μm thick) and polyethylene (50 μm thick), and hermetically sealed so as not to contain air. did. A 5 cm square cardboard colored in red was stuck on one side of the bag with an adhesive to obtain a temperature history recording indicator. When this was stored frozen at −20 ° C., it was frozen in 4 hours. Then, as a result of storing this at 20 degreeC, it thawed | decompressed in 5 minutes, oil layer isolation | separation expressed, and the red of cardboard was visually recognizable.

Example 10
5 g of the emulsified composition for temperature history recording obtained in Example 1 was made of nylon (15 μm thick), polyethylene (50 μm thick), one side of which was transparent and the other side was printed with a white-red houndstooth pattern. ) Laminate film bag (5 cm square) and hermetically sealed so as not to contain air to obtain an indicator for temperature history recording. When this was stored frozen at −20 ° C., it was frozen in 4 hours. Then, as a result of storing this at 20 ° C., it was thawed in 5 minutes, oil layer separation was developed, and a red-and-white houndstooth pattern printed on nylon was visible from one side.

  The emulsified composition for temperature history recording of the present invention undergoes demulsification upon freezing, and oil layer separation that is visible by thawing after demulsification occurs. Therefore, the emulsified composition for temperature history recording can be used as a temperature history recording indicator for recording a history of non-freezing, freezing, or thawing by enclosing the emulsion in a content-visible container. The present invention is preferably applicable to the distribution of goods that need to manage the temperature history of non-freezing, freezing, or thawing.

It is a figure which shows the state before freezing of the emulsion-like composition for temperature history recording. It is a figure which shows the state which frozen the emulsified composition for temperature history recording of FIG. 1 at -20 degreeC for 7 hours. It is a figure which shows the state which started defrosting the emulsion-form composition for temperature history recording of FIG. It is a figure which shows the state which thawed (melted) the emulsion-form composition for temperature history recording of FIG. It is a figure which shows an example of the indicator for temperature history recording of this invention. It is a figure which shows an example of the indicator for temperature history recording of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 50 Indicator for temperature history recording 51 Emulsified composition for temperature history recording 52 Flat bag 53 Surface protection member 54 Back surface protection member 55 Opening

Claims (17)

  An emulsified composition for temperature history recording that causes demulsification upon freezing and oil layer separation that is visible by thawing after demulsification, and includes vegetable oils and fats containing unsaturated fatty acids (excluding palm oil) and melting points An emulsified composition for temperature history recording, comprising palm oil of 25 ° C. or lower.   The emulsified composition for temperature history recording according to claim 1, wherein the vegetable oil and fat and palm oil are contained in a total amount of 40 to 80% by mass, and the mass ratio of the vegetable oil and palm oil is 2/1 to 50/1. object.   The emulsion composition for temperature history recording according to claim 1 or 2, wherein the pH is 5 or less.   The emulsified composition for temperature history recording according to claim 3, wherein the acidity in terms of acetic acid is 0.5 to 1% by mass and the salt concentration is 1.5 to 4% by mass.   Viscosity is 70-400 Pa.s, The emulsion composition for temperature history recording in any one of Claims 1-4.   The emulsion composition for temperature history recording according to any one of claims 1 to 4, which contains egg yolk and egg white so as not to exceed 5% by mass.   The emulsified composition for temperature history recording according to any one of claims 1 to 6, comprising xanthan gum.   When 5 g of the transparent resin film bag is filled and sealed so that substantially no head space is produced, it is demulsified upon freezing under the condition of storage at −20 ° C. for 10 hours. The emulsified composition for temperature history recording according to any one of claims 1 to 7, wherein oil layer separation that is visible is caused by thawing under conditions of storage at 10 ° C or higher for 30 minutes.   An indicator for temperature history recording, wherein the emulsion composition for temperature history recording according to any one of claims 1 to 8 is enclosed in a contents-visible container.   The temperature history recording indicator according to claim 9, wherein the contents-visible container is a flat bag made of a resin film, and at least a part of the resin film is transparent so that the contents can be visually recognized.   The resin film on both sides of the flat bag is transparent, and further has a front protective member and a back protective member arranged so as to sandwich the flat bag, and the flat protective bag can be observed from the outside on the surface protective member. The temperature history recording indicator according to claim 10, wherein an opening is provided.   The coloring and / or pattern which improves the visibility of oil layer separation which arises by the defrosting after the emulsion composition for temperature history recording demulsifies is printed on the flat bag side surface of a back surface protection member. Indicator for recording temperature history.   After the contents-visible container is a flat bag made of a resin film, one side of the flat bag is transparent so that the contents can be visually recognized, and the emulsion composition for temperature history recording is demulsified on the other side The temperature history recording indicator according to claim 9, wherein a color and / or pattern is printed so as to improve the visibility of oil layer separation caused by thawing.   A transportation slip equipped with the temperature history recording indicator according to claim 10.   The temperature management body with which the indicator for temperature history recording in any one of Claims 10-13 was mounted | worn.   A temperature history recording indicator according to any one of claims 10 to 13 is attached to a transportation slip, and the article to be transported with the transportation slip is unfrozen, frozen or thawed according to the presence or absence of oil layer separation of the indicator. How to determine the history of a job. 15. The transportation slip according to claim 14 or the temperature management body according to claim 15 is attached to an article, and then the article is distributed, and the temperature history recording attached to the transportation slip or the temperature management body at a predetermined distribution stage. A method for distributing goods, wherein it is determined whether or not an oil layer separation has occurred in an emulsified composition for temperature history recording enclosed in an indicator.

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