WO2017047648A1 - Cold insulation tool - Google Patents

Cold insulation tool Download PDF

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Publication number
WO2017047648A1
WO2017047648A1 PCT/JP2016/077127 JP2016077127W WO2017047648A1 WO 2017047648 A1 WO2017047648 A1 WO 2017047648A1 JP 2016077127 W JP2016077127 W JP 2016077127W WO 2017047648 A1 WO2017047648 A1 WO 2017047648A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
cold
inorganic salt
mass
indicator
Prior art date
Application number
PCT/JP2016/077127
Other languages
French (fr)
Japanese (ja)
Inventor
綾 内野
田中　康弘
Original Assignee
トッパン・フォームズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by トッパン・フォームズ株式会社 filed Critical トッパン・フォームズ株式会社
Priority to MYPI2018700757A priority Critical patent/MY186494A/en
Priority to CN201680052998.7A priority patent/CN108026435A/en
Priority to SG11201801341YA priority patent/SG11201801341YA/en
Publication of WO2017047648A1 publication Critical patent/WO2017047648A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D3/00—Devices using other cold materials; Devices using cold-storage bodies

Definitions

  • the present invention relates to a cold insulator provided with a cold insulating composition in which a color change during cooling can be easily visually recognized.
  • the cold insulator is widely used for cold storage during storage and transportation of various fresh products, and is usually used repeatedly.
  • a cold-retaining tool includes a cold-retaining composition having a cold-retaining action, and is configured by enclosing the cold-retaining composition in a thermally conductive container.
  • the composition for cold insulation those containing a colorant are known so that the presence thereof can be easily visually recognized from the outside of the cold insulation device.
  • the composition for cold insulation colored with a dye is enclosed.
  • a cold insulator whose disclosing amount can be easily confirmed from the outside is disclosed (see Patent Document 1).
  • the cold insulator described in Patent Document 1 is difficult to visually check the cooling state, such as the presence or absence of freezing, even if the cold-keeping composition contains a dye, and it is at a desired temperature that can be kept cold. There is a problem that the cold insulator is sufficiently cooled until it is difficult to visually check the cooling state.
  • This invention makes it a subject to provide the cooler which can be easily visually recognized whether a cooling state exists in the target state.
  • a first aspect of the present invention is a cold-retaining tool comprising a cold-retaining composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold-retaining composition is an aqueous solution thereof as the inorganic salt.
  • the ratio of the total content of the acidic inorganic salt and the phosphate to the total content of the inorganic salt Is 5 to 100% by mass
  • the composition for cold preservation contains, as the acidic inorganic salt, dihydrogen phosphate and an inorganic salt other than dihydrogen phosphate, and the pKa of the pH indicator is 4.9 to 8.0
  • the composition for cold preservation has a pH ( ⁇ 1) when all components other than phosphate, dihydrogen phosphate and water are removed, with respect to the pKa, It is a cold insulator that satisfies the relationship represented by the following formula (i).
  • pKa of pH indicator ⁇ pH ( ⁇ 1) ⁇ pKa of pH indicator + 1.8 (i)
  • the pH of the cold-retaining composition may be 4.6 to 8.8.
  • the cold-retaining composition has a pH ( ⁇ 3) of 6.0 to 8.5 when all the components other than the thickener and water are replaced with water. It may be a thing.
  • the second aspect of the present invention is a cold insulator provided with a cold-retaining composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold-retaining composition is used as the inorganic salt,
  • the aqueous solution contains an acidic inorganic salt that exhibits acidity, and monohydrogen phosphate, and in the cold insulation composition, the acidic inorganic salt and monohydrogen phosphate with respect to the total content of the inorganic salt
  • the ratio of the total content of is 5 to 100% by mass, and in the composition for cold preservation, the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt and the thickener is
  • the cold insulator is 0.2 to 5.0% by mass, and the pKa of the pH indicator is 4.9 to 8.0.
  • the pH of the cold-retaining composition may be 4.7 to 8.0.
  • the cold-retaining composition has a pH ( ⁇ 3) of 6.0 to 9.1 when all the components other than the thickener and water are replaced with water. It may be a thing.
  • the third aspect of the present invention is a cold insulator provided with a cold insulation composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold insulation composition is used as the inorganic salt,
  • the aqueous solution contains an acidic inorganic salt exhibiting acidity, and in the cold-retaining composition, the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass
  • the cold-retaining composition has a pH ( ⁇ 2) of 7 or less when all the components other than the inorganic salt and water are replaced with water, and the cold-retaining composition comprises the thickener and water.
  • PH ( ⁇ 3) is 7 or more when all other components are replaced with water, and the pH ( ⁇ 2) and pH ( ⁇ 3) are lower than the color change range of the pH indicator.
  • the pH ( ⁇ 2) and pH ( ⁇ 3) are lower than the color change range of the pH indicator.
  • the cold insulator of the present invention can be easily visually confirmed whether the cooling state is the target state.
  • the unit (ppm) of content (blending amount, concentration) is based on mass ratio unless otherwise specified.
  • the cold insulator according to the first embodiment of the present invention is a cold insulator provided with a cold insulating composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold insulating composition is the inorganic salt.
  • the acidic inorganic salt whose aqueous solution shows acidity and a phosphate.
  • the content ratio is 5 to 100% by mass
  • the composition for cold preservation contains, as the acidic inorganic salt, dihydrogen phosphate and an inorganic salt other than dihydrogen phosphate, and the pH
  • the pKa of the indicator is 4.9 to 8.0
  • the composition for cold preservation has a pH ( ⁇ 1) when all components other than phosphate, dihydrogen phosphate and water are removed.
  • the relationship represented by the following formula (i) is satisfied.
  • the color of the cold insulation composition of the cold insulation tool varies greatly before and after freezing of the cold insulation composition.
  • the color of the composition for cold preservation reflects the presence or absence of color development of the pH indicator. Therefore, the cold insulator can be easily visually confirmed whether the cooling state is in a target state (a state in which the object can be sufficiently cooled).
  • the color of the composition for cold preservation before and after freezing does not mainly reflect the color of components other than pH indicators, such as the said inorganic salt and a thickener.
  • the composition for cold preservation in the first embodiment contains an inorganic salt and a thickener as components that affect the acidity. And in the said composition for cold preservation, as said inorganic salt, inorganic salt other than dihydrogen phosphate which is acidic inorganic salt, dihydrogen phosphate which is acidic inorganic salt, and specification called phosphate These combinations are selected, the content of these inorganic salts is limited, and a pH indicator having a pKa in a specific range is used in combination with these inorganic salts.
  • the cold-retaining composition having such a configuration changes color remarkably greatly depending on the change in color presence or absence of the pH indicator.
  • the said inorganic salt in 1st Embodiment functions as one component of a cryogen, and the freezing temperature of the composition for cold preservation is mainly determined by the kind and quantity.
  • the inorganic salt is a component that does not correspond to the pH indicator, and precipitates as crystals or amorphous (amorphous) at the time of freezing of the cold insulation composition, and the color change of the cold insulation composition depends on the presence or absence of the precipitation. Involved in.
  • the composition for cold preservation in the first embodiment contains, as the inorganic salt, an acidic inorganic salt whose aqueous solution exhibits acidity and a phosphate, and further, as the acidic inorganic salt, dihydrogen phosphate. It contains salts and inorganic salts other than dihydrogen phosphate.
  • the dihydrogen phosphate used as the acidic inorganic salt is formed by replacing one hydrogen ion in phosphoric acid (H 3 PO 4 ) with a cation, and is non-hydrated. It may be a hydrate.
  • the dihydrogen phosphate in the first embodiment include sodium dihydrogen phosphate (NaH 2 PO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), and calcium dihydrogen phosphate (Ca (H 2 PO). 4 ) Dihydrogen phosphate metal salts such as 2 ); dihydrogen phosphate nonmetal salts such as ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), and the like.
  • 1 type may be sufficient as the dihydrogen phosphate which the composition for cold preservation in 1st Embodiment contains, and when it is 2 or more types and they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
  • the inorganic salt other than the dihydrogen phosphate used as the acidic inorganic salt is not particularly limited as long as the aqueous solution exhibits acidity, and may be a non-hydrate. Hydrates may also be used.
  • examples of inorganic salts other than the dihydrogen phosphate in the first embodiment include ammonium chloride (NH 4 Cl), magnesium chloride (MgCl 2 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), and ammonium nitrate (NH 4 ).
  • Al (SO 4 ) 3 aluminum sulfate (Al 2 (SO 4 ) 3 ), alum (AlK (SO 4 ) 2 ), ammonium alum (Al (NH 4 ) (SO 4 ) 2 ), calcium nitrate tetrahydrate (Ca ( NO 3 ) 2 ⁇ 4H 2 O), calcium nitrate (Ca (NO 3 ) 2 ) and the like, and ammonium chloride and ammonium nitrate are preferable.
  • the inorganic salt other than the dihydrogen phosphate contained in the composition for cold preservation in the first embodiment may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof are as follows: Can be arbitrarily selected.
  • the phosphate in the first embodiment is formed by replacing three hydrogen ions in phosphoric acid (H 3 PO 4 ) with a cation, and may be non-hydrated or hydrated. It may be a thing.
  • the phosphate is usually a basic salt whose aqueous solution shows basicity.
  • Examples of the phosphate in the first embodiment include trisodium phosphate (Na 3 PO 4 ), trisodium phosphate dodecahydrate (Na 3 PO 4 ⁇ 12H 2 O), and tripotassium phosphate (K 3 PO 4 ) triphosphates such as phosphate; triammonium phosphates such as triammonium phosphate ((NH 3 ) 3 PO 4 ), trisodium phosphate (Na 3 PO 4 ), phosphorus Trisodium acid dodecahydrate and tripotassium phosphate (K 3 PO 4 ) are preferred.
  • 1 type may be sufficient as the phosphate which the composition for cold preservation in 1st Embodiment contains, and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the composition for cold insulation in the first embodiment includes any of these as well.
  • Other inorganic salts not applicable may be contained.
  • the other inorganic salts may be non-hydrates or hydrates.
  • the said other inorganic salt in 1st Embodiment is not specifically limited unless the effect of this invention is impaired,
  • the neutral inorganic salt in which the aqueous solution shows neutrality
  • the phosphate in which the aqueous solution shows basicity
  • other inorganic salts for example, the neutral inorganic salt in which the aqueous solution shows neutrality, The phosphate in which the aqueous solution shows basicity And other inorganic salts.
  • the neutral inorganic salt examples include sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl 2 ), sodium sulfate (Na 2 SO 4 ), potassium sulfate (K 2 SO 4 ), and magnesium sulfate.
  • MgSO 4 sodium nitrate (NaNO 3 ), potassium nitrate (KNO 3 ), potassium bromide (KBr), sodium bromide (NaBr), potassium iodide (KI), sodium iodide (NaI), potassium chlorate ( KClO 3 ), sodium perchlorate (NaClO 4 ), sodium thiosulfate (Na 2 S 2 O 3 ) and the like.
  • the neutral inorganic salt is preferably sodium chloride or potassium chloride.
  • the basic inorganic salt other than the phosphate is preferably an inorganic salt other than monohydrogen phosphate, such as sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), and hydrogen carbonate.
  • examples include sodium (NaHCO 3 ), potassium hydrogen carbonate (KHCO 3 ), sodium sulfite (Na 2 SO 3 ), and borax (Na 2 B 4 O 7 ).
  • the basic inorganic salt other than the phosphate is preferably sodium carbonate or potassium carbonate.
  • the said other inorganic salt which the composition for cold preservation in 1st Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
  • the ratio of the total content of the acidic inorganic salt and the phosphate to the total content of the inorganic salt is 5 to 100% by mass, and 5.5 to It is preferable that it is 100 mass%.
  • the composition for cold preservation becomes large in the color change before and behind freezing.
  • the lower limit of the ratio for example, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 45% by mass and the like can be selected, but not limited thereto.
  • the upper limit value of the ratio can be selected from, for example, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, but is not limited thereto. .
  • the amount of the inorganic salt dissolved is preferably as large as possible, and the amount dissolved in the total amount of the inorganic salt is 90% by mass or more. Preferably, it is 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
  • the amount which has precipitated out of the total amount of the said inorganic salt is 90 mass% or more. 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
  • the total content of the inorganic salt in the cold-retaining composition is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and 15 to 25% by mass. Particularly preferred.
  • the said thickener in 1st Embodiment is a component which increases the viscosity of the composition for cold preservation, and does not correspond to the said pH indicator.
  • the thickener in the first embodiment is preferably one that does not precipitate when the composition for cold preservation is frozen.
  • “the thickener does not precipitate when the cryogenic composition is frozen” means that the thickener is solidified while being dissolved in water when the cryogenic composition is frozen, It is presumed that the thickener molecules are not solidified and are solidified while surrounded by water molecules, and the thickener molecules are not solidified by aggregation. Guessed.
  • acryl-type polymers compound which has polyacrylic acid frame
  • Carboxyalkyl such as carboxymethylcellulose (CMC) Cellulose
  • guar gum hydroxyalkyl guar gum such as hydroxypropyl guar gum
  • pectin xanthan gum
  • alkylene glycol such as propylene glycol.
  • the thickener in the first embodiment may be at least one selected from the group consisting of acrylic polymer, carboxyalkyl cellulose, xanthan gum, guar gum, hydroxyalkyl guar gum, pectin, tamarind gum, carrageenan and alkylene glycol. preferable.
  • the thickener is more preferably one or more selected from the group consisting of acrylic polymers, carboxyalkyl cellulose, xanthan gum, guar gum and hydroxyalkyl guar gum.
  • the thickener contained in the composition for cold insulation in the first embodiment may be only one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the amount of the thickener deposited is preferably as small as possible, and the amount deposited in the total amount of the thickener is 10% by mass or less. It is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 0% by mass (the total amount is not precipitated).
  • the content of the thickener in the composition for cold preservation is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and 0.6 to 3%. It is particularly preferable that the content is% by mass.
  • the pH indicator (acid-base indicator) in the first embodiment is a component that determines the color of the composition for cold preservation by reflecting the presence or absence of color development.
  • the composition for cold preservation changes a color before and after freezing by containing a pH indicator.
  • the pH indicator in the first embodiment is not particularly limited as long as it has a pKa of 4.9 to 8.0.
  • pKa of the pH indicator in this embodiment means the value in case a solvent is water and temperature is 25 degreeC.
  • the pH indicator has a pH range in which the color change is observed, that is, a color change range.
  • a pH indicator exists in a solution in a dissociated form and an undissociated form, and a dissociation equilibrium is established between them.
  • the dissociated form and the undissociated form have different colors. Then, the equilibrium is remarkably offset in either the dissociated form or the undissociated form, and only one color is seen.
  • the pH indicator is mixed in an amount that can be compared between the dissociated form and the undissociated form, and a mixture of both colors is observed ("Chemical Dictionary Dictionary 39th Edition, 2006 9"). May 15 ", Kyoritsu Publishing Co., Ltd.)).
  • Table 1 shows examples of main pH indicators. Table 1 shows the color change area and color change together with the pH indicator. “Color change (low pH ⁇ high pH)” in Table 1 means that the pH indicator changes when the pH of the liquid containing the pH indicator changes from a specific value to a higher value. For example, “red ⁇ yellow” means that the pH indicator changes the color of the liquid from red to yellow in the process of increasing the pH of the liquid.
  • the pH indicator in the first embodiment preferably has a color change range (pH) in the range of 3.0 to 10.5, more preferably in the range of 4.0 to 9.5. Particularly preferred are those in the range of 4.5 to 9.0.
  • 1 type may be sufficient as the pH indicator which the composition for cold preservation in 1st Embodiment contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily. However, it is usually preferable to contain only one kind of pH indicator.
  • the content of the pH indicator in the cold-retaining composition in the first embodiment is not particularly limited as long as the intended color change of the cold-retaining composition is achieved, but is preferably 1 to 30 ppm, and is preferably 5 to 20 ppm. More preferably.
  • the composition for cold preservation in 1st Embodiment may contain the other component which does not correspond to these in the range which does not impair the effect of this invention other than water, an inorganic salt, a thickener, and a pH indicator.
  • the other components include solvents other than water; various known additives such as preservatives and surfactants.
  • the said other component which the composition for cold preservation in 1st Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the solvent in the first embodiment is preferably one that can dissolve the inorganic salt, thickener, and pH indicator, and examples of such a solvent include alcohol.
  • the freezing temperature of the cryopreservation composition is determined mainly by the type and amount thereof.
  • the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less. 2% by mass or less is particularly preferable.
  • preservative examples include food preservatives, antioxidants, and the like. More specifically, sodium pyrithione, paraben (paraoxybenzoic acid ester), protamine, organic nitrogen sulfur-based compound, and the like. Is mentioned.
  • the content of the preservative in the composition for cold preservation in the first embodiment is not particularly limited, but is preferably 0.02 to 0.5% by mass, and preferably 0.04 to 0.2% by mass. More preferred.
  • surfactant examples include known ones such as alkyl sulfates such as sodium dodecyl sulfate; alkyl carboxylates such as sodium decanoate; N-alkyl acrylamides such as N-isopropylacrylamide.
  • Polyoxyethylene dialkyl ethers such as polyoxyethylene octyldodecyl ether; polyoxyethylene monoalkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene monoalkenyl ethers such as polyoxyethylene oleyl ether;
  • the composition for cold preservation in 1st Embodiment is the said inorganic salt, increase with respect to the total content of components other than water and the said solvent (The said inorganic salt, a thickener, a pH indicator, and other components other than the said solvent).
  • the ratio of the total content of the adhesive and the pH indicator is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 96% by mass or more, and 98% by mass or more. It is particularly preferable that it may be 100% by mass.
  • the ratio of the total content is equal to or higher than the lower limit value, the color of the cold-retaining composition changes more greatly before and after freezing.
  • the pH ( ⁇ 1) when all the components other than phosphate, dihydrogen phosphate and water are removed is expressed by the following formula (pKa) of the pH indicator: The relationship represented by i) is satisfied.
  • pH ( ⁇ 1) is a mixed solution (for example, phosphate) obtained by mixing only the same amount of phosphate, dihydrogen phosphate and water as the amount contained in the composition for cold preservation in the first embodiment.
  • pH of an aqueous solution containing dihydrogen phosphate serves as an index of the acidity of the mixture of phosphate and dihydrogen phosphate used in the cold insulation composition.
  • the pH ( ⁇ 1) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the temperature of the mixed solution is 25 ° C.
  • the pH ( ⁇ 1) preferably further satisfies 5.0 to 10.6, more preferably 5.3 to 10.3, while satisfying the relationship of the above formula (i). Particularly preferred is 6 to 10.0.
  • the pH of the composition for cold preservation in the first embodiment is preferably 4.6 to 8.8, more preferably 4.9 to 8.5, and 5.1 to 8.3. Is particularly preferred.
  • the composition for cold preservation in the first embodiment preferably exhibits a pH in the numerical range at a temperature at which the pH indicator is dissolved in the composition for cold preservation, and the temperature of the composition for cold insulation is 25 ° C. Sometimes it is more preferred to exhibit a pH in the numerical range.
  • description with mere "pH" about the composition for cold preservation shall mean the pH of the composition for cold preservation itself unless there is particular notice.
  • the composition for cold preservation in the first embodiment preferably has a pH ( ⁇ 2) of 4.4 to 8.7 when all the components other than the inorganic salt and water are replaced with water. More preferably, it is ⁇ 8.2.
  • the pH ( ⁇ 2) corresponds to the pH of an inorganic salt-containing water (for example, an inorganic salt aqueous solution) containing only the inorganic salt at the same content (mass%) as the content (mass%) in the composition for cold preservation. To do.
  • the pH ( ⁇ 2) serves as an index of the acidity of the inorganic salt used in the cold insulation composition.
  • the pH ( ⁇ 2) is preferably the pH at the temperature at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the inorganic salt-containing water is 25 ° C.
  • the composition for cold preservation in the first embodiment preferably has a pH ( ⁇ 3) of 6.0 to 8.5 when all the components other than the thickener and water are replaced with water. It is more preferably from 0 to 8.3, for example, from 6.0 to 8.0, or from 6.5 to 7.5.
  • pH ( ⁇ 3) is the same as the content (mass%) in the cold insulation composition (mass%) of the thickener-containing water (eg, thickener aqueous solution) containing only the thickener.
  • the pH ( ⁇ 3) serves as an index of the acidity of the thickener used in the cold insulation composition.
  • the pH ( ⁇ 3) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the thickener-containing water is 25 ° C. .
  • the composition for cold preservation in 1st Embodiment is obtained by mix
  • the blending method of each component is not particularly limited, and can be arbitrarily adjusted so that each component is uniformly dissolved or dispersed at a temperature higher than the freezing temperature of the composition for cold preservation. For example, when blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, and all components may be mixed while being added sequentially. May be.
  • the mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.
  • the cold insulation tool according to the first embodiment of the present invention is provided with the cold insulation composition.
  • the cold insulation composition is held by a holding means such as a container or bag that can enclose a liquid material. It is composed by doing.
  • the material of the holding means is not particularly limited as long as the holding means has transparency to such an extent that the color change (discoloration) of the held cold insulating composition is visible.
  • preferable holding means include polyolefins such as polyethylene and polypropylene; polyamides; synthetic resins such as polyesters and the like.
  • polyethylene include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE).
  • the material and size of the holding means may be selected in consideration of, for example, the shape of the holding means, the amount of the cold-retaining composition held, or how the color of the cold-retaining composition changes before and after freezing.
  • a preferable material of the holding means in the case of a bag-shaped holding means, is low density polyethylene.
  • an example of a preferable material for the holding means is high-density polyethylene.
  • the bag-like holding means is preferable when it is used as a small one, that is, when the amount of the cold-retaining composition is relatively small.
  • the container-like holding means is preferable when it is used as a large one, that is, when the amount of the cold-retaining composition is relatively large.
  • the method for selecting the material and size of the holding means shown here is merely an example.
  • the material of the holding means is preferably polyolefin in terms of excellent low temperature brittleness resistance, water resistance and chemical resistance, and is high density polyethylene in terms of easy molding and high strength. It is more preferable.
  • the thickness of the flat part such as a film or sheet in the holding means is not particularly limited, but is preferably 5 to 200 ⁇ m.
  • the flat part may be composed of a single layer or may be composed of two or more layers.
  • the plurality of layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be the same. And when several layers differ from each other, the combination of these several layers is not specifically limited.
  • the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
  • the total thickness of each layer is preferably the thickness of the preferred flat part.
  • the composition for cold preservation in the first embodiment largely changes in color before and after freezing, the presence or absence of freezing can be easily visually confirmed. And this color change of the composition for cold insulation is visible from the outer side of a cold insulator. Thereby, it is possible to easily visually check whether the cold insulator is sufficiently cooled to a desired temperature.
  • the effect of the cold-retaining composition is not impaired even when the cooling and heating are repeated, such as repeated freezing and thawing. Therefore, the cold insulator provided with the cold-retaining composition is also suitable for repeated use.
  • the cold insulation device is a cold insulation device provided with a cold insulation composition containing water, an inorganic salt, a thickener, and a pH indicator, wherein the cold insulation composition is the inorganic salt.
  • the aqueous solution contains an acidic inorganic salt that exhibits acidity and monohydrogen phosphate, and in the composition for cold preservation, the acidic inorganic salt and monobasic phosphate with respect to the total content of the inorganic salt
  • the ratio of the total content of hydrogen salt is 5 to 100% by mass
  • the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt and the thickener in the composition for cold preservation Is 0.2 to 5.0% by mass
  • the pKa of the pH indicator is 4.9 to 8.0.
  • the color of the cold insulation composition of the cold insulation tool varies greatly before and after freezing of the cold insulation composition.
  • the color of the composition for cold preservation reflects the presence or absence of color development of the pH indicator. Therefore, the cold insulator can be easily visually confirmed whether the cooling state is in a target state (a state in which the object can be sufficiently cooled).
  • the color of the composition for cold preservation before and after freezing does not mainly reflect the color of components other than pH indicators, such as the said inorganic salt and a thickener.
  • the composition for cold preservation in the second embodiment contains an inorganic salt and a thickener as components that affect the acidity.
  • an inorganic salt a specific combination of an acidic inorganic salt and a monohydrogen phosphate is selected, the content of these inorganic salts is limited, and the monohydrogen phosphate is The ratio of the content to the total content of water, inorganic salt, and thickener is also limited, and a pH indicator having a pKa in a specific range is used in combination with these inorganic salt and thickener.
  • the cold-retaining composition having such a configuration changes color remarkably greatly depending on the change in color presence or absence of the pH indicator.
  • the said inorganic salt in 2nd Embodiment functions as one component of a cryoprotectant, and the freezing temperature of the composition for cold preservation is mainly determined by the kind and quantity.
  • the inorganic salt is a component that does not correspond to the pH indicator, and precipitates as crystals or amorphous (amorphous) at the time of freezing of the cold insulation composition, and the color change of the cold insulation composition depends on the presence or absence of the precipitation. Involved in.
  • the said composition for cold preservation in 2nd Embodiment contains the acidic inorganic salt in which the aqueous solution shows acidity, and monohydrogen phosphate as said inorganic salt.
  • the acidic inorganic salt in the second embodiment is not particularly limited and can be appropriately selected depending on the purpose, and may be a non-hydrate or a hydrate.
  • As an acidic inorganic salt in 2nd Embodiment the same thing as the said acidic inorganic salt in 1st Embodiment, ie, inorganic salts other than dihydrogen phosphate and dihydrogen phosphate, is mentioned, for example. .
  • the acidic inorganic salt contained in the composition for cold insulation in the second embodiment may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. .
  • the monohydrogen phosphate in the second embodiment is obtained by replacing two hydrogen ions in phosphoric acid (H 3 PO 4 ) with a cation, and may be a non-hydrate, Hydrates may also be used.
  • the monohydrogen phosphate is generally a basic salt whose aqueous solution shows basicity.
  • Examples of the monohydrogen phosphate in the second embodiment include phosphorus such as disodium hydrogen phosphate (Na 2 HPO 4 ), dipotassium hydrogen phosphate (K 2 HPO 4 ), and calcium hydrogen phosphate (CaHPO 4 ). Examples thereof include metal monohydrogen phosphate; non-metal monohydrogen phosphate such as diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ).
  • 1 type of phosphoric acid monohydrogen salt which the composition for cold preservation in 2nd Embodiment contains may be one, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
  • composition for cold preservation in 2nd Embodiment may contain the other inorganic salt which does not correspond to any of these other than the said acidic inorganic salt and phosphoric acid monohydrogen salt as said inorganic salt.
  • the other inorganic salts may be non-hydrates or hydrates.
  • the said other inorganic salt in 2nd Embodiment is not specifically limited unless the effect of this invention is impaired,
  • the neutral inorganic salt in which the aqueous solution shows neutrality
  • the phosphoric acid one in which the aqueous solution shows basicity examples include inorganic salts other than hydrogen salts.
  • Examples of the neutral inorganic salt include the same neutral inorganic salt as in the first embodiment, and sodium chloride, potassium chloride, or sodium sulfate is preferable.
  • the basic inorganic salt other than the phosphate monobasic salt is preferably an inorganic salt other than a phosphate, and for example, the same basic inorganic salt other than the phosphate in the first embodiment may be used. And is preferably sodium carbonate or potassium carbonate.
  • the said other inorganic salt which the composition for cold preservation in 2nd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
  • Preferred examples of the cold-retaining composition in the second embodiment include those containing the dihydrogen phosphate salt, which is the acidic inorganic salt, and a neutral inorganic salt. Such a cold-retaining composition has a shorter time required for completion of the color change before and after freezing and has more preferable properties.
  • the neutral inorganic salt is preferably sodium chloride or potassium chloride.
  • the ratio of the content of neutral inorganic salt to the total content of inorganic salt is 40 to 60.
  • the content is preferably mass%, more preferably 43 to 57 mass%, particularly preferably 46 to 54 mass%.
  • the ratio is in such a range, the composition for cold preservation in the second embodiment completes a color change in a shorter time and undergoes a greater color change before and after freezing.
  • content (mass) of dihydrogen phosphate with respect to content (mass) of monohydrogen phosphate ) Ratio ([content of dihydrogen phosphate in the composition for cold insulation (mass)] / [content of monohydrogen phosphate in the composition for cold insulation (mass)]) is 0.04 to 2 It is preferably 0.04 to 1.6, more preferably 0.04 to 1.4.
  • the ratio is in such a range, the color change of the composition for cold insulation in the second embodiment is completed in a shorter time before and after freezing.
  • the ratio is preferably 0.04 to 1.2, preferably 0.07 to 0.8. Is more preferable, and 0.1 to 0.6 is particularly preferable.
  • the ratio of the total content of the acidic inorganic salt and monohydrogen phosphate to the total content of the inorganic salt is 5 to 100% by mass.
  • the content is preferably 5 to 100% by mass, more preferably 6 to 100% by mass.
  • the composition for cold preservation becomes large in the color change before and behind freezing.
  • the lower limit of the ratio for example, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 45% by mass and the like can be selected, but not limited thereto.
  • the upper limit value of the ratio for example, 90% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass and the like can be selected, but not limited thereto. .
  • the amount of the inorganic salt dissolved is preferably as large as possible, and the amount dissolved in the total amount of the inorganic salt is 90% by mass or more. Preferably, it is 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
  • the amount which has precipitated among the total amount of the said inorganic salt is 90 mass% or more. 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
  • the total content of the inorganic salt of the composition for cold insulation is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, and 10 to 30% by mass. More preferably, for example, it may be 15 to 25% by mass.
  • the said thickener in 2nd Embodiment is a component which increases the viscosity of the composition for cold preservation, and does not correspond to the said pH indicator.
  • the thickener in the second embodiment is preferably one that does not precipitate when the composition for cold preservation is frozen. In the present specification, “the thickener does not precipitate when the composition for cold preservation is frozen” is as described above in the first embodiment.
  • the thickener in 2nd Embodiment is selected from the group consisting of acrylic polymer, carboxyalkyl cellulose, xanthan gum, guar gum, hydroxyalkyl guar gum, pectin, tamarind gum, carrageenan and alkylene glycol. It is preferable that it is 1 or more types selected.
  • the thickener is more preferably one or more selected from the group consisting of acrylic polymers, carboxyalkyl cellulose, xanthan gum, guar gum and hydroxyalkyl guar gum.
  • the thickener contained in the composition for cold insulation in the second embodiment may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the amount of the thickener deposited is preferably as small as possible, and the amount deposited in the total amount of the thickener is 10% by mass or less. It is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 0% by mass (the total amount is not precipitated).
  • the content of the thickener in the composition for cold preservation is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and 0.6 to 3%. It is particularly preferable that the content is% by mass.
  • the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt, and the thickener is 0.2 to 5.0% by mass. 0.23 to 4.9% by mass, more preferably 0.26 to 4.8% by mass.
  • the ratio is in such a range, the color change before and after freezing increases in the composition for cold preservation.
  • the pH indicator (acid-base indicator) in the second embodiment is a component that determines the color of the composition for cold preservation by reflecting the presence or absence of color development.
  • the composition for cold preservation changes a color before and after freezing by containing a pH indicator.
  • the pH indicator in the second embodiment is not particularly limited as long as it has a pKa of 4.9 to 8.0.
  • pKa of the pH indicator in this embodiment means the value in case a solvent is water and temperature is 25 degreeC.
  • As said pH indicator in 2nd Embodiment the same thing as the pH indicator in 1st Embodiment is mentioned, for example.
  • the pH indicator in the second embodiment preferably has a color change range (pH) in the range of 3.0 to 9.0, more preferably in the range of 4.0 to 8.5. Particularly preferred are those in the range of 4.5 to 8.0.
  • the pH indicator contained in the composition for cold preservation in the second embodiment may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. However, it is usually preferable to contain only one kind of pH indicator.
  • the content of the pH indicator in the cold insulation composition in the second embodiment is not particularly limited as long as the intended color change of the cold insulation composition is achieved, but is preferably 1 to 30 ppm, and preferably 5 to 20 ppm. More preferably.
  • the composition for cold preservation in 2nd Embodiment may contain the other component which does not correspond to these in the range which does not impair the effect of this invention other than water, an inorganic salt, a thickener, and a pH indicator.
  • the other components include the same solvents other than water as in the first embodiment; various known additives such as preservatives and surfactants.
  • the said other component which the composition for cold preservation in 2nd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the content of the other components in the cold insulation composition in the second embodiment is the same as the content of the other components in the cold insulation composition in the first embodiment.
  • the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, and preferably 5% by mass or less. More preferred is 2% by mass or less.
  • the content of the preservative in the composition for cold preservation in the second embodiment is not particularly limited, but is preferably 0.02 to 0.5% by mass, and 0.04 to 0.2% by mass. It is more preferable.
  • the composition for cold preservation in 2nd Embodiment is the said inorganic salt and increase with respect to the total content of components other than water and the said solvent (The said inorganic salt, a thickener, a pH indicator, and other components other than the said solvent).
  • the ratio of the total content of the adhesive and the pH indicator is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 96% by mass or more, and 98% by mass or more. It is particularly preferable that it may be 100% by mass.
  • the ratio of the total content is equal to or higher than the lower limit value, the color of the cold-retaining composition changes more greatly before and after freezing.
  • the pH of the cold-retaining composition in the second embodiment is preferably 4.7 to 8.0, more preferably 5.0 to 7.7, and 5.2 to 7.5. Is particularly preferred. It is preferable that the composition for cold preservation in 2nd Embodiment shows pH of the said numerical range at the temperature which the pH indicator melt
  • the composition for cold preservation in the second embodiment preferably has a pH ( ⁇ 2) of 4.7 to 8.0 when all the components other than the inorganic salt and water are replaced with water. More preferably, it is ⁇ 7.5.
  • the pH ( ⁇ 2) corresponds to the pH of an inorganic salt-containing water (for example, an inorganic salt aqueous solution) containing only the inorganic salt at the same content (mass%) as the content (mass%) in the composition for cold preservation. To do.
  • the pH ( ⁇ 2) serves as an index of the acidity of the inorganic salt used in the cold insulation composition.
  • the pH ( ⁇ 2) is preferably the pH at the temperature at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the inorganic salt-containing water is 25 ° C.
  • the composition for cold preservation in the second embodiment preferably has a pH ( ⁇ 3) of 6.0 to 9.1 when all the components other than the thickener and water are replaced with water. More preferably, it is 5 to 8.6. pH ( ⁇ 3) is the same as the content (mass%) in the cold insulation composition (mass%) of the thickener-containing water (eg, thickener aqueous solution) containing only the thickener. Corresponds to pH.
  • the pH ( ⁇ 3) serves as an index of the acidity of the thickener used in the cold insulation composition.
  • the pH ( ⁇ 3) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the thickener-containing water is 25 ° C. .
  • composition for cold preservation in the second embodiment is obtained by the same method as the composition for cold insulation in the first embodiment described above, except that the blending components are different.
  • the cold insulation tool according to the second embodiment of the present invention includes the cold insulation composition, and has the same configuration as the cold insulation tool according to the first embodiment except that the cold insulation composition is different. can do.
  • the cold insulator according to the second embodiment of the present invention is obtained by the same method as the cold insulator according to the first embodiment described above, except that the cold insulation composition is used.
  • the composition for cold preservation in the second embodiment largely changes in color before and after freezing, the presence or absence of freezing can be easily visually confirmed. And this color change of the composition for cold insulation is visible from the outer side of a cold insulator. Thereby, it is possible to easily visually check whether the cold insulator is sufficiently cooled to a desired temperature. The effect of the cold-retaining composition is not impaired even when the cooling and heating are repeated, such as repeated freezing and thawing. Therefore, the cold insulator provided with the cold-retaining composition is also suitable for repeated use.
  • the cold insulation tool according to the third embodiment of the present invention is a cold insulation tool provided with a cold insulation composition containing water, an inorganic salt, a thickener, and a pH indicator, wherein the cold insulation composition is the inorganic salt.
  • the aqueous solution contains an acidic inorganic salt exhibiting acidity, and in the composition for cold preservation, the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass.
  • the cold-retaining composition has a pH ( ⁇ 2) of 7 or less when all the components other than the inorganic salt and water are replaced with water, and the cold-retaining composition is the thickener PH ( ⁇ 3) when all components other than water and water are replaced with water is 7 or more, and pH ( ⁇ 2) and pH ( ⁇ 3) are lower than the color change range of the pH indicator, discoloration Of the three pH ranges, the pH of the range and the pH higher than the color change range, Shows the different values of pH range are.
  • the color of the cold insulation composition of the cold insulation tool varies greatly before and after freezing of the cold insulation composition.
  • the color of the composition for cold preservation reflects the presence or absence of color development of the pH indicator. Therefore, the cold insulator can be easily visually confirmed whether the cooling state is in a target state (a state in which the object can be sufficiently cooled).
  • the color of the composition for cold preservation before and after freezing does not mainly reflect the color of components other than pH indicators, such as the said inorganic salt and a thickener.
  • the composition for cold preservation in the third embodiment contains an inorganic salt and a thickener as components that affect the acidity. And in the composition for cold preservation, an acidic inorganic salt is selected as the inorganic salt, the content is limited, the acidity of the inorganic salt and the thickener is limited, and these inorganic salts and thickeners are further limited.
  • a pH indicator having a suitable color change range is used in combination with the agent. The cold-retaining composition having such a configuration changes color remarkably greatly depending on the change in color presence or absence of the pH indicator.
  • the said inorganic salt in 3rd Embodiment functions as one component of a cryogen, and the freezing temperature of the composition for cold preservation is mainly determined by the kind and quantity.
  • the inorganic salt is a component that does not correspond to the pH indicator, and precipitates as crystals or amorphous (amorphous) at the time of freezing of the cold insulation composition, and the color change of the cold insulation composition depends on the presence or absence of the precipitation. Involved in.
  • the said composition for cold preservation in 3rd Embodiment contains the acidic inorganic salt in which the aqueous solution shows acidity as said inorganic salt.
  • the acidic inorganic salt in the third embodiment is not particularly limited and can be appropriately selected depending on the purpose, and may be a non-hydrate or a hydrate.
  • Preferable acidic inorganic salts in the third embodiment are, for example, the same inorganic salts other than dihydrogen phosphate in the first embodiment, that is, ammonium chloride (NH 4 Cl), magnesium chloride (MgCl 2 ).
  • Ammonium sulfate (NH 4 ) 2 SO 4 ), ammonium nitrate (NH 4 NO 3 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), alum (AlK (SO 4 ) 2 ), ammonium alum (Al (NH 4) ) (SO 4 ) 2 ), calcium nitrate tetrahydrate (Ca (NO 3 ) 2 .4H 2 O), calcium nitrate (Ca (NO 3 ) 2 ) and the like, and ammonium chloride is preferred.
  • the acidic inorganic salt contained in the composition for cold preservation in the third embodiment may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. .
  • composition for cold preservation in 3rd Embodiment may contain other inorganic salt other than the said acidic inorganic salt as said inorganic salt.
  • the other inorganic salts may be non-hydrates or hydrates.
  • the other inorganic salt in the third embodiment is not particularly limited as long as the effects of the present invention are not impaired.
  • the neutral inorganic salt whose aqueous solution shows neutrality and the basic salt whose aqueous solution shows basicity.
  • An inorganic salt etc. are mentioned.
  • Examples of the neutral inorganic salt include the same neutral inorganic salt as in the first embodiment, and sodium chloride or potassium chloride is preferable.
  • the basic inorganic salt is preferably an inorganic salt other than phosphate and monohydrogen phosphate, and examples thereof include the same basic inorganic salts other than the phosphate in the first embodiment. And is preferably sodium carbonate or potassium carbonate.
  • the said other inorganic salt which the composition for cold preservation in 3rd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
  • the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass, for example, 20 to 80% by mass, 40% It can be set to ⁇ 60% by mass, but is not limited thereto.
  • the lower limit of the ratio in addition to 20% by mass and 40% by mass, for example, 10% by mass, 30% by mass, 45% by mass, etc. can be selected.
  • the upper limit value of the ratio for example, 90% by mass, 70% by mass, 55% by mass and the like can be selected in addition to the above 80% by mass and 60% by mass. However, it is not limited to these.
  • the amount of the inorganic salt dissolved is preferably as large as possible, and the amount dissolved in the total amount of the inorganic salt is 90% by mass or more. Preferably, it is 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
  • the amount which has precipitated among the total amount of the said inorganic salt is 90 mass% or more. 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
  • the total content of the inorganic salt of the composition for cold insulation is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and 15 to 25% by mass. Particularly preferred.
  • the thickener in the third embodiment is a component that increases the viscosity of the cold-retaining composition and does not correspond to the pH indicator.
  • the thickener in the third embodiment is preferably one that does not precipitate when the composition for cold preservation is frozen. In the present specification, “the thickener does not precipitate when the composition for cold preservation is frozen” is as described above in the first embodiment.
  • the thickener in 3rd Embodiment is selected from the group consisting of acrylic polymer, carboxyalkyl cellulose, xanthan gum, guar gum, hydroxyalkyl guar gum, pectin, tamarind gum, carrageenan and alkylene glycol. It is preferable that it is 1 or more types selected.
  • the thickener is more preferably one or more selected from the group consisting of acrylic polymers, carboxyalkyl cellulose, xanthan gum, guar gum and hydroxyalkyl guar gum.
  • the thickener contained in the composition for cold insulation in the third embodiment may be only one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the amount of the thickener deposited is preferably as small as possible, and the amount deposited in the total amount of the thickener is 10% by mass or less. It is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 0% by mass (the total amount is not precipitated).
  • the content of the thickener in the composition for cold preservation is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and 0.6 to 3%. It is particularly preferable that the content is% by mass.
  • the pH indicator (acid-base indicator) in the third embodiment is a component that determines the color of the composition for cold preservation by reflecting the presence or absence of color development.
  • the composition for cold preservation changes a color before and after freezing by containing a pH indicator.
  • the pH indicator in the third embodiment is not particularly limited, but preferably has a pKa of 4.0 to 7.5.
  • pKa of the pH indicator in this embodiment means the value in case a solvent is water and temperature is 25 degreeC.
  • As said pH indicator in 3rd Embodiment the same thing as the pH indicator in 1st Embodiment is mentioned, for example.
  • the pH indicator in the third embodiment preferably has a color change range (pH) in the range of 3.0 to 10.5, more preferably in the range of 3.3 to 9.5. And those in the range of 3.5 to 9.0 are particularly preferred.
  • the pH indicator contained in the composition for cold preservation in the third embodiment may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. However, it is usually preferable to contain only one kind of pH indicator.
  • the content of the pH indicator in the cold insulation composition in the third embodiment is not particularly limited as long as the intended color change of the cold insulation composition is achieved, but is preferably 1 to 30 ppm, and is preferably 5 to 20 ppm. More preferably.
  • the composition for cold preservation in 3rd Embodiment may contain the other component which does not correspond to these in the range which does not impair the effect of this invention other than water, an inorganic salt, a thickener, and a pH indicator.
  • the other components include the same solvents other than water as in the first embodiment; various known additives such as preservatives and surfactants.
  • the said other component which the composition for cold preservation in 3rd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the content of the other components in the cold insulation composition in the third embodiment is the same as the content of the other components in the cold insulation composition in the first embodiment.
  • the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, and preferably 5% by mass or less. More preferred is 2% by mass or less.
  • the content of the preservative in the composition for cold preservation in the third embodiment is not particularly limited, but is preferably 0.02 to 0.5% by mass, and 0.04 to 0.2% by mass. It is more preferable.
  • the composition for cold preservation in the third embodiment includes the inorganic salt, the increase in the total content of components other than water and the solvent (the inorganic salt, the thickener, the pH indicator, and other components other than the solvent).
  • the ratio of the total content of the adhesive and the pH indicator is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 96% by mass or more, and 98% by mass or more. It is particularly preferable that it may be 100% by mass.
  • the ratio of the total content is equal to or higher than the lower limit value, the color of the cold-retaining composition changes more greatly before and after freezing.
  • the composition for cold preservation in the third embodiment has a pH ( ⁇ 2) of 7 or less when all the components other than the inorganic salt and water are replaced with water.
  • the pH ( ⁇ 2) corresponds to the pH of an inorganic salt-containing water (for example, an inorganic salt aqueous solution) containing only the inorganic salt at the same content (mass%) as the content (mass%) in the composition for cold preservation. To do.
  • the pH ( ⁇ 2) serves as an index of the acidity of the inorganic salt used in the cold insulation composition.
  • the pH ( ⁇ 2) is preferably 3.5 to 7.0, more preferably 4.0 to 6.6, and particularly preferably 4.5 to 6.3.
  • the pH ( ⁇ 2) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the inorganic salt-containing water is 25 ° C.
  • the composition for cold preservation in the third embodiment has a pH ( ⁇ 3) of 7 or more when all the components other than the thickener and water are replaced with water.
  • pH ( ⁇ 3) is the same as the content (mass%) in the cold insulation composition (mass%) of the thickener-containing water (eg, thickener aqueous solution) containing only the thickener.
  • the pH ( ⁇ 3) serves as an index of the acidity of the thickener used in the cold insulation composition.
  • the pH ( ⁇ 3) is preferably from 7.0 to 9.5, more preferably from 7.0 to 9.0, and particularly preferably from 7.0 to 8.5.
  • the pH ( ⁇ 3) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the thickener-containing water is 25 ° C. .
  • the composition for cold preservation in the third embodiment has three pH ranges in which pH ( ⁇ 2) and pH ( ⁇ 3) are lower than the color change range of the pH indicator, the pH of the color change range, and the pH higher than the color change range. Among them, values in different pH ranges are shown.
  • the pH of the cold-retaining composition in the third embodiment is preferably 4.1 to 7.4, more preferably 4.4 to 7.1, and 4.6 to 6.9. Is particularly preferred.
  • the cold-retaining composition in the third embodiment preferably exhibits a pH in the numerical range at a temperature at which the pH indicator is dissolved in the cold-retaining composition, and the temperature of the cold-retaining composition is 25 ° C. Sometimes it is more preferred to exhibit a pH in the numerical range.
  • description with mere "pH" about the composition for cold preservation shall mean the pH of the composition for cold preservation itself unless there is particular notice.
  • composition for cold insulation in the third embodiment is obtained by the same method as the composition for cold insulation in the first embodiment described above, except that the blending components are different.
  • the cold insulation tool according to the third embodiment of the present invention is provided with the cold insulation composition, and has the same configuration as the cold insulation tool according to the first embodiment except that the cold insulation composition is different. can do.
  • the cold insulator according to the third embodiment of the present invention is obtained by the same method as the cold insulator according to the first embodiment described above, except that the cold insulating composition is used.
  • the composition for cold preservation in the third embodiment largely changes in color before and after freezing, the presence or absence of freezing can be easily visually confirmed. And this color change of the composition for cold insulation is visible from the outer side of a cold insulator. Thereby, it is possible to easily visually check whether the cold insulator is sufficiently cooled to a desired temperature. The effect of the cold-retaining composition is not impaired even when the cooling and heating are repeated, such as repeated freezing and thawing. Therefore, the cold insulator provided with the cold-retaining composition is also suitable for repeated use.
  • PH indicator Bromocresol purple (Wako Pure Chemical Industries, Ltd.)
  • PR Phenol red (manufactured by Wako Pure Chemical Industries)
  • BTB Bromothymol Blue (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MR Methyl Red (manufactured by Wako Pure Chemical Industries)
  • BCG Bromocresol Green (Wako Pure Chemical Industries, Ltd.) (Preservative) "Sodium Omagine" manufactured by Sanai Oil Co., Ltd.
  • Example 1 Manufacture of composition for cold preservation and cold insulation tool (first embodiment)> Under room temperature (20-25 ° C.), BCP was added and dissolved in water (79.16 parts by mass), and then ammonium chloride (9.72 parts by mass), potassium chloride (9.72 parts by mass), Trisodium phosphate dodecahydrate (0.15 parts by mass) and ammonium dihydrogen phosphate (0.10 parts by mass) were added and dissolved, and then HPG1 (1.10 parts by mass) was added. The mixture was stirred for 1 hour at room temperature and dissolved, and after confirming that the obtained liquid was sufficiently thickened, an antiseptic (0.05 parts by mass) was added, The composition for cold preservation was obtained by stirring for 30 minutes.
  • the compounding quantity of BCP was adjusted so that content in the obtained composition for cold preservation might be 8 ppm.
  • Table 2 shows the content of each compounding component and its composition for cold storage.
  • “basic salt” in the column of the blending component means a basic salt other than phosphate and monohydrogen phosphate.
  • trisodium phosphate dodecahydrate is described by omitting crystal water (12H 2 O). The same applies to the following tables.
  • Table 7 shows physical properties such as pH ( ⁇ 1), pH ( ⁇ 2), pH ( ⁇ 3), pH indicator pKa when the solvent is water and the temperature is 25 ° C., and the pH of the composition for cold preservation.
  • the pH ( ⁇ 1), pH ( ⁇ 2), pH ( ⁇ 3) and the pH were all measured with the temperature of the measurement object being 25 ° C.
  • the ratio of the total content of the acidic inorganic salt and the phosphate to the total content of the inorganic salt in the obtained composition for cold insulation hereinafter, this value may be indicated by the symbol “(X1)”) Table 7 shows.
  • the obtained cold insulation composition was sealed in a container made of high density polyethylene to obtain the cold insulation tool of the first embodiment.
  • color change described in the evaluation result column indicates a color change of the cold-retaining composition before and after freezing.
  • green ⁇ yellow means a cold-retaining composition. Indicates that the color was green before freezing and yellow after freezing.
  • ⁇ The color change before and after freezing is large and the cooling state is very easy to visually recognize.
  • delta The color change before and behind freezing can be discriminate
  • X The color change before and after freezing is unclear, and it is difficult or impossible to visually recognize the cooling state.
  • “low pH ⁇ high pH color change” described in the column of the color change region of the pH indicator means that the pH of the liquid containing the pH indicator is higher than a specific value.
  • the pH indicator changes to a value, the pH indicator shows the color change within the color change range.
  • “yellow ⁇ purple” means that the pH indicator changes the color of the liquid from yellow to purple in the process of increasing the pH of the liquid. Indicates to change.
  • composition for cold preservation and cold insulation tool evaluation of composition for cold insulation> [Examples 2 to 13]
  • the composition for cold insulation and the cold insulation of the first embodiment are the same as those of Example 1, except that the components of the cold insulation composition and the content in the cold insulation composition are as shown in Tables 2 and 3.
  • a tool was manufactured and a cold insulation composition was evaluated.
  • Table 7 shows the physical properties of the cold insulation composition, and Table 9 shows the evaluation results.
  • Example 14 ⁇ Manufacture of composition for cold preservation and cold insulation tool (second embodiment)> Under room temperature (20 to 25 ° C.), BCP is added and dissolved in water (78.90 parts by mass), and then ammonium chloride (9.70 parts by mass), potassium chloride (9.70 parts by mass) and Obtained by adding diammonium hydrogen phosphate (0.50 parts by mass) and then dissolving CMC (1.10 parts by mass) while stirring at room temperature for 1 hour After confirming that the liquid was sufficiently thickened, a preservative (0.05 parts by mass) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a composition for cold preservation. At this time, the compounding quantity of BCP was adjusted so that content in the obtained composition for cold preservation might be 8 ppm. Table 3 shows the content of each compounding component and its composition for cold storage.
  • Table 7 shows physical properties such as pH ( ⁇ 1), pH ( ⁇ 2), pH ( ⁇ 3), pH indicator pKa when the solvent is water and the temperature is 25 ° C., and the pH of the composition for cold preservation.
  • the pH ( ⁇ 1), pH ( ⁇ 2), pH ( ⁇ 3) and the pH were all measured with the temperature of the measurement object being 25 ° C.
  • Ratio of total content of acidic inorganic salt and monohydrogen phosphate with respect to the total content of inorganic salt in the obtained composition for cold insulation (hereinafter, this value may be indicated by “(X2)”) ), And the ratio of the content of monohydrogen phosphate to the total content of water, inorganic salt and thickener (hereinafter, this value may be indicated by the symbol “(X3)”) is also shown in Table 7. ing.
  • the obtained cold insulation composition was sealed in a container made of high-density polyethylene to obtain a cold insulation tool of the second embodiment.
  • composition for cold preservation and cold insulation tool evaluation of composition for cold insulation> [Examples 15 to 33]
  • a cold insulation tool was manufactured, and the composition for cold insulation was evaluated.
  • the physical properties of the composition for cold preservation are shown in Tables 7 to 8, and the evaluation results are shown in Table 9, respectively.
  • Example 34 ⁇ Manufacture of a composition for cold preservation and a cold insulation tool (third embodiment)> At room temperature (20 to 25 ° C.), MR is added and dissolved in water (79.35 parts by mass), and then ammonium chloride (9.75 parts by mass) and potassium chloride (9.75 parts by mass) are added. Then, CMC (1.10 parts by mass) was added and stirred for 1 hour at room temperature to dissolve, and it was confirmed that the obtained liquid was sufficiently thickened. Thereafter, a preservative (0.05 parts by mass) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a composition for cold preservation. At this time, the blending amount of MR was adjusted so that the content in the obtained cold insulation composition was 8 ppm. Table 5 shows the content of each compounding component and its composition for cold storage.
  • Table 8 shows physical properties such as pH ( ⁇ 1), pH ( ⁇ 2), pH ( ⁇ 3), pH indicator pKa when the solvent is water and the temperature is 25 ° C., and the pH of the composition for cold preservation.
  • the pH ( ⁇ 1), pH ( ⁇ 2), pH ( ⁇ 3) and the pH were all measured with the temperature of the measurement object being 25 ° C.
  • Table 8 also shows the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt in the obtained cold-retaining composition (hereinafter, this value may be indicated by “(X4)”). Yes.
  • the obtained cold insulation composition was sealed in a container made of high density polyethylene to obtain the cold insulation tool of the third embodiment.
  • composition for cold preservation and cold insulation tool evaluation of composition for cold insulation> [Examples 35 to 37]
  • the composition for cold insulation and the cold insulation tool of the third embodiment were the same as in Example 34 except that the components of the cold insulation composition and the content in the cold insulation composition were as shown in Table 5. And the composition for cold preservation was evaluated.
  • Table 8 shows the physical properties of the cold insulation composition, and Table 9 shows the evaluation results.
  • composition for cold insulation ⁇ Manufacture of composition for cold preservation and cold insulation, evaluation of composition for cold insulation> [Comparative Examples 1 to 9] A composition for cold insulation and a cold insulation tool were produced in the same manner as in Example 1 except that the components in the cold insulation composition and the content in the cold insulation composition were as shown in Tables 5 and 6, The composition for cold preservation was evaluated. Table 8 shows the physical properties of the cold insulation composition, and Table 9 shows the evaluation results.
  • the cold insulator according to the first embodiment of the present invention (Examples 1 to 13), the cold insulator according to the second embodiment (Examples 14 to 33), and the cold insulator according to the third embodiment.
  • the composition for cold preservation was colored before and after freezing, reflecting the change in color development of the pH indicator with the precipitation of inorganic salts during freezing of the composition for cold preservation. Changed clearly, and the cooling state could be easily visually confirmed.
  • the time required for completing the color change of the cold insulation composition was short, and particularly preferable properties were exhibited. .
  • the time required for completion of the color change of the cold insulation composition was short, and particularly preferable properties were exhibited. This has shown that there exists a tendency which shows such a preferable property, when the composition for cold preservation contains a dihydrogen phosphate salt and a neutral inorganic salt.
  • the cold insulation composition is different from that in the above examples, the color change is unclear before and after freezing, and the cooling state is visually recognized. Was difficult or impossible.
  • composition for cold preservation and cold insulation tool evaluation of composition for cold insulation> [Examples 38 to 40]
  • the composition for cold insulation and the cold insulation tool of the first embodiment were the same as in Example 1 except that the composition components of the cold insulation composition and the content in the cold insulation composition were as shown in Table 10.
  • Manufactured and evaluated compositions for cold storage Table 11 shows the physical properties of the cold insulation composition, and Table 12 shows the evaluation results.
  • composition for cold preservation and cold insulation tool (second embodiment), evaluation of composition for cold insulation> [Examples 41 to 46]
  • the composition for cold insulation and the cold insulation tool of the second embodiment were the same as in Example 14, except that the components of the cold insulation composition and the content in the cold insulation composition were as shown in Table 10.
  • Manufactured and evaluated compositions for cold storage Table 11 shows the physical properties of the cold insulation composition, and Table 12 shows the evaluation results.
  • the present invention can be used as a cold insulator for various fresh foods.

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Abstract

This cold insulation tool is provided with a cold insulation composition containing water, an inorganic salt, a thickening agent, and a pH indicator, wherein: the cold insulation composition contains, as the inorganic salt, a phosphate and an acidic inorganic salt of which the aqueous solution exhibits acidity; in the cold insulation composition, the proportion of the total contained amount of the phosphate and the acidic inorganic salt with respect to the total contained amount of the inorganic salt is 5-100 mass%; the cold insulation composition contains, as the acidic inorganic salt, a dihydrogen phosphate and an inorganic salt other than the dihydrogen phosphate; pKa of the pH indicator is 4.9-8.0; in the cold insulation composition, pH (α1) obtained when all the contained components except for the phosphate, dihydrogen phosphate, and water are removed satisfies the relationship represented by formula (i) with respect to the pKa. pKa of pH indicator ≤ pH (α1) ≤ 1.8 + pKa of pH indicator ····(i)

Description

保冷具Cooler
　本発明は、冷却時の色変化が容易に視認可能な保冷用組成物を備えた保冷具に関する。
　本願は、２０１５年９月１８日に、日本に出願された特願２０１５－１８５０４３号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a cold insulator provided with a cold insulating composition in which a color change during cooling can be easily visually recognized.
This application claims priority based on Japanese Patent Application No. 2015-185043 filed in Japan on September 18, 2015, the contents of which are incorporated herein by reference.
　保冷具は、各種生鮮物の保管時や輸送時の保冷に幅広く利用されており、通常は、繰り返して利用される。このような保冷具は、保冷作用を有する保冷用組成物を備え、熱伝導性を有する容器中にこの保冷用組成物が封入されて、構成される。
　保冷用組成物としては、その存在が保冷具の外側から容易に視認可能となるように、着色剤を含有するものが知られており、例えば、染料により着色された保冷用組成物が封入され、その封入量が外部から容易に確認可能となっている保冷具が開示されている（特許文献１参照）。 The cold insulator is widely used for cold storage during storage and transportation of various fresh products, and is usually used repeatedly. Such a cold-retaining tool includes a cold-retaining composition having a cold-retaining action, and is configured by enclosing the cold-retaining composition in a thermally conductive container.
As the composition for cold insulation, those containing a colorant are known so that the presence thereof can be easily visually recognized from the outside of the cold insulation device. For example, the composition for cold insulation colored with a dye is enclosed. A cold insulator whose disclosing amount can be easily confirmed from the outside is disclosed (see Patent Document 1).
　しかし、特許文献１に記載の保冷具は、保冷用組成物が染料を含有していても、凍結の有無など、冷却状態を目視により確認することは困難であり、保冷可能な所望の温度にまで保冷具が十分に冷却されているか、冷却状態の視認が困難であるという問題点があった。 However, the cold insulator described in Patent Document 1 is difficult to visually check the cooling state, such as the presence or absence of freezing, even if the cold-keeping composition contains a dye, and it is at a desired temperature that can be kept cold. There is a problem that the cold insulator is sufficiently cooled until it is difficult to visually check the cooling state.
特開２００６－９７９８４号公報JP 2006-97984 A
　本発明は、冷却状態が目的とする状態にあるか容易に視認可能な保冷具を提供することを課題とする。 This invention makes it a subject to provide the cooler which can be easily visually recognized whether a cooling state exists in the target state.
　本発明の第１の態様は、水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸塩と、を含有し、前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸塩の合計含有量の割合が、５～１００質量％であり、前記保冷用組成物が、前記酸性の無機塩として、リン酸二水素塩とリン酸二水素塩以外の無機塩とを含有し、前記ｐＨ指示薬のｐＫａが４．９～８．０であり、前記保冷用組成物は、リン酸塩、リン酸二水素塩及び水以外の含有成分をすべて除去した場合のｐＨ（α１）が、前記ｐＫａに対して、下記式（ｉ）で表される関係を満たすものである、保冷具である。
　ｐＨ指示薬のｐＫａ≦ｐＨ（α１）≦ｐＨ指示薬のｐＫａ＋１．８　・・・・（ｉ） A first aspect of the present invention is a cold-retaining tool comprising a cold-retaining composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold-retaining composition is an aqueous solution thereof as the inorganic salt. In the composition for cold preservation, the ratio of the total content of the acidic inorganic salt and the phosphate to the total content of the inorganic salt Is 5 to 100% by mass, and the composition for cold preservation contains, as the acidic inorganic salt, dihydrogen phosphate and an inorganic salt other than dihydrogen phosphate, and the pKa of the pH indicator is 4.9 to 8.0, and the composition for cold preservation has a pH (α1) when all components other than phosphate, dihydrogen phosphate and water are removed, with respect to the pKa, It is a cold insulator that satisfies the relationship represented by the following formula (i).
pKa of pH indicator ≦ pH (α1) ≦ pKa of pH indicator + 1.8 (i)
　本発明の第１の態様においては、前記保冷用組成物のｐＨが４．６～８．８であってもよい。
　本発明の第１の態様においては、前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が、６．０～８．５となるものでもよい。 In the first aspect of the present invention, the pH of the cold-retaining composition may be 4.6 to 8.8.
In the first aspect of the present invention, the cold-retaining composition has a pH (α3) of 6.0 to 8.5 when all the components other than the thickener and water are replaced with water. It may be a thing.
　また、本発明の第２の態様は、水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸一水素塩と、を含有し、前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸一水素塩の合計含有量の割合が、５～１００質量％であり、前記保冷用組成物において、水、前記無機塩及び増粘剤の総含有量に対する、リン酸一水素塩の含有量の割合が、０．２～５．０質量％であり、前記ｐＨ指示薬のｐＫａが４．９～８．０である、保冷具である。 Moreover, the second aspect of the present invention is a cold insulator provided with a cold-retaining composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold-retaining composition is used as the inorganic salt, The aqueous solution contains an acidic inorganic salt that exhibits acidity, and monohydrogen phosphate, and in the cold insulation composition, the acidic inorganic salt and monohydrogen phosphate with respect to the total content of the inorganic salt The ratio of the total content of is 5 to 100% by mass, and in the composition for cold preservation, the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt and the thickener is The cold insulator is 0.2 to 5.0% by mass, and the pKa of the pH indicator is 4.9 to 8.0.
　本発明の第２の態様においては、前記保冷用組成物のｐＨが４．７～８．０であってもよい。
　本発明の第２の態様においては、前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が、６．０～９．１となるものでもよい。 In the second aspect of the present invention, the pH of the cold-retaining composition may be 4.7 to 8.0.
In the second aspect of the present invention, the cold-retaining composition has a pH (α3) of 6.0 to 9.1 when all the components other than the thickener and water are replaced with water. It may be a thing.
　また、本発明の第３の態様は、水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩を含有し、前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩の含有量の割合が、５～１００質量％であり、前記保冷用組成物は、前記無機塩及び水以外の含有成分をすべて水で置換した場合のｐＨ（α２）が７以下となるものであり、前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が７以上となるものであり、ｐＨ（α２）及びｐＨ（α３）が、前記ｐＨ指示薬の変色域よりも低いｐＨ、変色域のｐＨ、及び変色域よりも高いｐＨの３つのｐＨ域のうち、互いに異なるｐＨ域の値を示す、保冷具である。 Moreover, the third aspect of the present invention is a cold insulator provided with a cold insulation composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold insulation composition is used as the inorganic salt, The aqueous solution contains an acidic inorganic salt exhibiting acidity, and in the cold-retaining composition, the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass, The cold-retaining composition has a pH (α2) of 7 or less when all the components other than the inorganic salt and water are replaced with water, and the cold-retaining composition comprises the thickener and water. PH (α3) is 7 or more when all other components are replaced with water, and the pH (α2) and pH (α3) are lower than the color change range of the pH indicator. Of the three pH ranges of pH and pH higher than the color change range, It indicates the value of pH range which makes a cold tool.
　本発明の保冷具は、冷却状態が目的とする状態にあるか容易に視認可能である。 The cold insulator of the present invention can be easily visually confirmed whether the cooling state is the target state.
　本発明の保冷具の好ましい例について以下に説明する。ただし、本発明はこれら例のみに限定されることはなく、例えば、本発明の趣旨を逸脱しない範囲で、追加、省略、置換、及びその他の変更（量、数、位置、サイズなど）が可能である。 A preferred example of the cold insulator of the present invention will be described below. However, the present invention is not limited to these examples. For example, additions, omissions, substitutions, and other changes (amount, number, position, size, etc.) are possible without departing from the spirit of the present invention. It is.
　なお、本明細書において、含有量（配合量、濃度）の単位「ｐｐｍ」は、特に断りのない限り、すべて質量比に基づくものである。 In this specification, the unit (ppm) of content (blending amount, concentration) is based on mass ratio unless otherwise specified.
＜＜第１実施形態＞＞
　本発明の第１実施形態に係る保冷具は、水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸塩と、を含有し、前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸塩の合計含有量の割合が、５～１００質量％であり、前記保冷用組成物が、前記酸性の無機塩として、リン酸二水素塩とリン酸二水素塩以外の無機塩とを含有し、前記ｐＨ指示薬のｐＫａが４．９～８．０であり、前記保冷用組成物は、リン酸塩、リン酸二水素塩及び水以外の含有成分をすべて除去した場合のｐＨ（α１）が、前記ｐＫａに対して、下記式（ｉ）で表される関係を満たす。
　ｐＨ指示薬のｐＫａ≦ｐＨ（α１）≦ｐＨ指示薬のｐＫａ＋１．８　・・・・（ｉ） << First Embodiment >>
The cold insulator according to the first embodiment of the present invention is a cold insulator provided with a cold insulating composition containing water, an inorganic salt, a thickener and a pH indicator, wherein the cold insulating composition is the inorganic salt. As the total amount of the acidic inorganic salt and the phosphate with respect to the total content of the inorganic salt in the composition for cold preservation, the acidic inorganic salt whose aqueous solution shows acidity and a phosphate. The content ratio is 5 to 100% by mass, and the composition for cold preservation contains, as the acidic inorganic salt, dihydrogen phosphate and an inorganic salt other than dihydrogen phosphate, and the pH The pKa of the indicator is 4.9 to 8.0, and the composition for cold preservation has a pH (α1) when all components other than phosphate, dihydrogen phosphate and water are removed. On the other hand, the relationship represented by the following formula (i) is satisfied.
pKa of pH indicator ≦ pH (α1) ≦ pKa of pH indicator + 1.8 (i)
　前記保冷具の保冷用組成物の色は、保冷用組成物の凍結の前後において大きく変化する。ここで、保冷用組成物の色は、ｐＨ指示薬の発色の有無が反映されたものである。そのため、前記保冷具は、冷却状態が目的とする状態（対象物を十分に冷却できる状態）にあるか容易に視認可能となっている。そして、凍結の前後における保冷用組成物の色は、前記無機塩、増粘剤等のｐＨ指示薬以外の含有成分自体の色を主として反映したものではない。 The color of the cold insulation composition of the cold insulation tool varies greatly before and after freezing of the cold insulation composition. Here, the color of the composition for cold preservation reflects the presence or absence of color development of the pH indicator. Therefore, the cold insulator can be easily visually confirmed whether the cooling state is in a target state (a state in which the object can be sufficiently cooled). And the color of the composition for cold preservation before and after freezing does not mainly reflect the color of components other than pH indicators, such as the said inorganic salt and a thickener.
　第１実施形態における保冷用組成物は、その酸性度に影響を与える成分として、無機塩及び増粘剤を含有する。そして、前記保冷用組成物においては、前記無機塩として、酸性の無機塩であるリン酸二水素塩と、酸性の無機塩であるリン酸二水素塩以外の無機塩と、リン酸塩という特定の組み合わせを選択し、これら無機塩の含有量を限定し、さらにこれら無機塩に対して、ｐＫａが特定範囲にあるｐＨ指示薬を組み合わせて用いている。このような構成を有する前記保冷用組成物は、ｐＨ指示薬の発色の変化又は有無に依存して、顕著に大きく色変化する。 The composition for cold preservation in the first embodiment contains an inorganic salt and a thickener as components that affect the acidity. And in the said composition for cold preservation, as said inorganic salt, inorganic salt other than dihydrogen phosphate which is acidic inorganic salt, dihydrogen phosphate which is acidic inorganic salt, and specification called phosphate These combinations are selected, the content of these inorganic salts is limited, and a pH indicator having a pKa in a specific range is used in combination with these inorganic salts. The cold-retaining composition having such a configuration changes color remarkably greatly depending on the change in color presence or absence of the pH indicator.
＜無機塩＞
　第１実施形態における前記無機塩は、保冷剤の一成分として機能し、主にその種類及び量により、保冷用組成物の凍結温度が決定される。
　また、前記無機塩は、前記ｐＨ指示薬に該当しない成分であり、保冷用組成物の凍結時に、結晶又はアモルファス（非晶質）として析出し、その析出の有無によって、保冷用組成物の色変化に関与する。 <Inorganic salt>
The said inorganic salt in 1st Embodiment functions as one component of a cryogen, and the freezing temperature of the composition for cold preservation is mainly determined by the kind and quantity.
The inorganic salt is a component that does not correspond to the pH indicator, and precipitates as crystals or amorphous (amorphous) at the time of freezing of the cold insulation composition, and the color change of the cold insulation composition depends on the presence or absence of the precipitation. Involved in.
　第１実施形態における前記保冷用組成物は、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸塩と、を含有し、さらに前記酸性の無機塩として、リン酸二水素塩とリン酸二水素塩以外の無機塩とを含有する。 The composition for cold preservation in the first embodiment contains, as the inorganic salt, an acidic inorganic salt whose aqueous solution exhibits acidity and a phosphate, and further, as the acidic inorganic salt, dihydrogen phosphate. It contains salts and inorganic salts other than dihydrogen phosphate.
［酸性の無機塩］
（リン酸二水素塩）
　第１実施形態において、前記酸性の無機塩として用いるリン酸二水素塩は、リン酸（Ｈ３ＰＯ４）中の１個の水素イオンがカチオンで置換されてなるものであり、非水和物であってもよいし、水和物であってもよい。
　第１実施形態におけるリン酸二水素塩としては、例えば、リン酸二水素ナトリウム（ＮａＨ２ＰＯ４）、リン酸二水素カリウム（ＫＨ２ＰＯ４）、リン酸二水素カルシウム（Ｃａ（Ｈ２ＰＯ４）２）等のリン酸二水素金属塩；リン酸二水素アンモニウム（ＮＨ４Ｈ２ＰＯ４）等のリン酸二水素非金属塩等が挙げられる。 [Acid inorganic salt]
(Dihydrogen phosphate)
In the first embodiment, the dihydrogen phosphate used as the acidic inorganic salt is formed by replacing one hydrogen ion in phosphoric acid (H 3 PO 4 ) with a cation, and is non-hydrated. It may be a hydrate.
Examples of the dihydrogen phosphate in the first embodiment include sodium dihydrogen phosphate (NaH 2 PO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), and calcium dihydrogen phosphate (Ca (H 2 PO). 4 ) Dihydrogen phosphate metal salts such as 2 ); dihydrogen phosphate nonmetal salts such as ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), and the like.
　第１実施形態における保冷用組成物が含有するリン酸二水素塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 1 type may be sufficient as the dihydrogen phosphate which the composition for cold preservation in 1st Embodiment contains, and when it is 2 or more types and they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
（リン酸二水素塩以外の無機塩）
　第１実施形態において、前記酸性の無機塩として用いる、リン酸二水素塩以外の無機塩は、その水溶液が酸性を示すものであれば特に限定されず、非水和物であってもよいし、水和物であってもよい。
　第１実施形態における前記リン酸二水素塩以外の無機塩としては、例えば、塩化アンモニウム（ＮＨ４Ｃｌ）、塩化マグネシウム（ＭｇＣｌ２）、硫酸アンモニウム（（ＮＨ４）２ＳＯ４）、硝酸アンモニウム（ＮＨ４ＮＯ３）、硫酸アルミニウム（Ａｌ２（ＳＯ４）３）、ミョウバン（ＡｌＫ（ＳＯ４）２）、アンモニウムミョウバン（Ａｌ（ＮＨ４）（ＳＯ４）２）、硝酸カルシウム四水和物（Ｃａ（ＮＯ３）２・４Ｈ２Ｏ）、硝酸カルシウム（Ｃａ（ＮＯ３）２）等が挙げられ、塩化アンモニウム、硝酸アンモニウムが好ましい。 (Inorganic salts other than dihydrogen phosphate)
In the first embodiment, the inorganic salt other than the dihydrogen phosphate used as the acidic inorganic salt is not particularly limited as long as the aqueous solution exhibits acidity, and may be a non-hydrate. Hydrates may also be used.
Examples of inorganic salts other than the dihydrogen phosphate in the first embodiment include ammonium chloride (NH 4 Cl), magnesium chloride (MgCl 2 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), and ammonium nitrate (NH 4 ). NO 3 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), alum (AlK (SO 4 ) 2 ), ammonium alum (Al (NH 4 ) (SO 4 ) 2 ), calcium nitrate tetrahydrate (Ca ( NO 3 ) 2 · 4H 2 O), calcium nitrate (Ca (NO 3 ) 2 ) and the like, and ammonium chloride and ammonium nitrate are preferable.
　第１実施形態における保冷用組成物が含有するリン酸二水素塩以外の無機塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The inorganic salt other than the dihydrogen phosphate contained in the composition for cold preservation in the first embodiment may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof are as follows: Can be arbitrarily selected.
［リン酸塩］
　第１実施形態における前記リン酸塩は、リン酸（Ｈ３ＰＯ４）中の３個の水素イオンがカチオンで置換されてなるものであり、非水和物であってもよいし、水和物であってもよい。
　前記リン酸塩は、通常、その水溶液が塩基性を示す塩基性の塩である。 [Phosphate]
The phosphate in the first embodiment is formed by replacing three hydrogen ions in phosphoric acid (H 3 PO 4 ) with a cation, and may be non-hydrated or hydrated. It may be a thing.
The phosphate is usually a basic salt whose aqueous solution shows basicity.
　第１実施形態におけるリン酸塩としては、例えば、リン酸三ナトリウム（Ｎａ３ＰＯ４）、リン酸三ナトリウム十二水和物（Ｎａ３ＰＯ４・１２Ｈ２Ｏ）、リン酸三カリウム（Ｋ３ＰＯ４）等のリン酸三金属塩；リン酸三アンモニウム（（ＮＨ３）３ＰＯ４）等のリン酸三非金属塩等が挙げられ、リン酸三ナトリウム（Ｎａ３ＰＯ４）、リン酸三ナトリウム十二水和物、リン酸三カリウム（Ｋ３ＰＯ４）が好ましい。 Examples of the phosphate in the first embodiment include trisodium phosphate (Na 3 PO 4 ), trisodium phosphate dodecahydrate (Na 3 PO 4 · 12H 2 O), and tripotassium phosphate (K 3 PO 4 ) triphosphates such as phosphate; triammonium phosphates such as triammonium phosphate ((NH 3 ) 3 PO 4 ), trisodium phosphate (Na 3 PO 4 ), phosphorus Trisodium acid dodecahydrate and tripotassium phosphate (K 3 PO 4 ) are preferred.
　第１実施形態における保冷用組成物が含有するリン酸塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 1 type may be sufficient as the phosphate which the composition for cold preservation in 1st Embodiment contains, and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
［その他の無機塩］
　第１実施形態における保冷用組成物は、前記無機塩として、前記酸性の無機塩（リン酸二水素塩及びリン酸二水素塩以外の無機塩）並びにリン酸塩以外に、これらのいずれにも該当しないその他の無機塩を含有していてもよい。
　前記その他の無機塩は、非水和物であってもよいし、水和物であってもよい。 [Other inorganic salts]
In addition to the acidic inorganic salt (inorganic salt other than dihydrogen phosphate and dihydrogen phosphate) and phosphate as the inorganic salt, the composition for cold insulation in the first embodiment includes any of these as well. Other inorganic salts not applicable may be contained.
The other inorganic salts may be non-hydrates or hydrates.
　第１実施形態における前記その他の無機塩は、本発明の効果を損なわない限り特に限定されないが、例えば、その水溶液が中性を示す中性の無機塩、その水溶液が塩基性を示すリン酸塩以外の無機塩等が挙げられる。 Although the said other inorganic salt in 1st Embodiment is not specifically limited unless the effect of this invention is impaired, For example, the neutral inorganic salt in which the aqueous solution shows neutrality, The phosphate in which the aqueous solution shows basicity And other inorganic salts.
　前記中性の無機塩としては、例えば、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）、塩化カルシウム（ＣａＣｌ２）、硫酸ナトリウム（Ｎａ２ＳＯ４）、硫酸カリウム（Ｋ２ＳＯ４）、硫酸マグネシウム（ＭｇＳＯ４）、硝酸ナトリウム（ＮａＮＯ３）、硝酸カリウム（ＫＮＯ３）、臭化カリウム（ＫＢｒ）、臭化ナトリウム（ＮａＢｒ）、ヨウ化カリウム（ＫＩ）、ヨウ化ナトリウム（ＮａＩ）、塩素酸カリウム（ＫＣｌＯ３）、過塩素酸ナトリウム（ＮａＣｌＯ４）、チオ硫酸ナトリウム（Ｎａ２Ｓ２Ｏ３）等が挙げられる。
　これらの中でも、前記中性の無機塩は、塩化ナトリウム又は塩化カリウムであることが好ましい。 Examples of the neutral inorganic salt include sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl 2 ), sodium sulfate (Na 2 SO 4 ), potassium sulfate (K 2 SO 4 ), and magnesium sulfate. (MgSO 4 ), sodium nitrate (NaNO 3 ), potassium nitrate (KNO 3 ), potassium bromide (KBr), sodium bromide (NaBr), potassium iodide (KI), sodium iodide (NaI), potassium chlorate ( KClO 3 ), sodium perchlorate (NaClO 4 ), sodium thiosulfate (Na 2 S 2 O 3 ) and the like.
Among these, the neutral inorganic salt is preferably sodium chloride or potassium chloride.
　前記リン酸塩以外の塩基性の無機塩は、リン酸一水素塩以外の無機塩であることが好ましく、例えば、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸水素ナトリウム（ＮａＨＣＯ３）、炭酸水素カリウム（ＫＨＣＯ３）、亜硫酸ナトリウム（Ｎａ２ＳＯ３）、ホウ砂（Ｎａ２Ｂ４Ｏ７）等が挙げられる。
　これらの中でも、前記リン酸塩以外の塩基性の無機塩は、炭酸ナトリウム又は炭酸カリウムであることが好ましい。 The basic inorganic salt other than the phosphate is preferably an inorganic salt other than monohydrogen phosphate, such as sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), and hydrogen carbonate. Examples include sodium (NaHCO 3 ), potassium hydrogen carbonate (KHCO 3 ), sodium sulfite (Na 2 SO 3 ), and borax (Na 2 B 4 O 7 ).
Among these, the basic inorganic salt other than the phosphate is preferably sodium carbonate or potassium carbonate.
　第１実施形態における保冷用組成物が含有する前記その他の無機塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The said other inorganic salt which the composition for cold preservation in 1st Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
　第１実施形態での保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸塩の合計含有量の割合は、５～１００質量％であり、５．５～１００質量％であることが好ましい。前記割合が前記下限値以上であることで、保冷用組成物は、凍結の前後における色変化が大きくなる。
　このような数値範囲の中で、前記割合の下限値としては、例えば、１０質量％、２０質量％、３０質量％、４０質量％、４５質量％等が選択できるが、これらに限定されない。また、このような数値範囲の中で、前記割合の上限値としては、例えば、９０質量％、８０質量％、７０質量％、６０質量％、５５質量％等が選択できるが、これらに限定されない。 In the composition for cold preservation in the first embodiment, the ratio of the total content of the acidic inorganic salt and the phosphate to the total content of the inorganic salt is 5 to 100% by mass, and 5.5 to It is preferable that it is 100 mass%. When the said ratio is more than the said lower limit, the composition for cold preservation becomes large in the color change before and behind freezing.
In such a numerical range, as the lower limit of the ratio, for example, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 45% by mass and the like can be selected, but not limited thereto. Further, in such a numerical range, the upper limit value of the ratio can be selected from, for example, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, but is not limited thereto. .
　第１実施形態における凍結前、好ましくは０℃以上の保冷用組成物中で、前記無機塩の溶解量は多いほど好ましく、前記無機塩の総量のうち溶解している量が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがさらに好ましく、１００質量％（全量）であってもよい。
　また、第１実施形態における凍結後の保冷用組成物中で、前記無機塩の析出量は多いほど好ましく、前記無機塩の総量のうち析出している量が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがさらに好ましく、１００質量％（全量）であってもよい。 Before freezing in the first embodiment, preferably in the cold-retaining composition at 0 ° C. or higher, the amount of the inorganic salt dissolved is preferably as large as possible, and the amount dissolved in the total amount of the inorganic salt is 90% by mass or more. Preferably, it is 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
Moreover, in the composition for cold preservation after freezing in 1st Embodiment, it is so preferable that there is much precipitation amount of the said inorganic salt, and it is preferable that the amount which has precipitated out of the total amount of the said inorganic salt is 90 mass% or more. 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
　第１実施形態における保冷用組成物の無機塩の総含有量は、５～３５質量％であることが好ましく、１０～３０質量％であることがより好ましく、１５～２５質量％であることが特に好ましい。 In the first embodiment, the total content of the inorganic salt in the cold-retaining composition is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and 15 to 25% by mass. Particularly preferred.
＜増粘剤＞
　第１実施形態における前記増粘剤は、保冷用組成物の粘度を増大させ、前記ｐＨ指示薬に該当しない成分である。第１実施形態における前記増粘剤は、保冷用組成物の凍結時に析出しないものが好ましい。なお、本明細書において「増粘剤が保冷用組成物の凍結時に析出しない」とは、保冷用組成物の凍結時に、増粘剤が水に溶解した状態のまま固化することを意味し、増粘剤の分子が多量に集合することなく、水分子に取り囲まれたまま固化している状態であると推測され、多量の増粘剤の分子が集合して固化している状態ではないと推測される。 <Thickener>
The said thickener in 1st Embodiment is a component which increases the viscosity of the composition for cold preservation, and does not correspond to the said pH indicator. The thickener in the first embodiment is preferably one that does not precipitate when the composition for cold preservation is frozen. In the present specification, “the thickener does not precipitate when the cryogenic composition is frozen” means that the thickener is solidified while being dissolved in water when the cryogenic composition is frozen, It is presumed that the thickener molecules are not solidified and are solidified while surrounded by water molecules, and the thickener molecules are not solidified by aggregation. Guessed.
　第１実施形態における前記増粘剤としては、特に限定されないが、例えば、ポリアクリル酸、ポリアクリル酸ナトリウム等のアクリル系ポリマー（ポリアクリル酸骨格有する化合物）；カルボキシメチルセルロース（ＣＭＣ）等のカルボキシアルキルセルロース；グアーガム；ヒドロキシプロピルグアーガム等のヒドロキシアルキルグアーガム；ペクチン；キサンタンガム；タマリンドガム；カラギーナン；プロピレングリコール等のアルキレングリコール等が挙げられる。 Although it does not specifically limit as said thickener in 1st Embodiment, For example, acryl-type polymers (compound which has polyacrylic acid frame | skeleton), such as polyacrylic acid and sodium polyacrylate; Carboxyalkyl, such as carboxymethylcellulose (CMC) Cellulose; guar gum; hydroxyalkyl guar gum such as hydroxypropyl guar gum; pectin; xanthan gum; tamarind gum; carrageenan; alkylene glycol such as propylene glycol.
　第１実施形態における前記増粘剤は、アクリル系ポリマー、カルボキシアルキルセルロース、キサンタンガム、グアーガム、ヒドロキシアルキルグアーガム、ペクチン、タマリンドガム、カラギーナン及びアルキレングリコールからなる群から選択される１種以上であることが好ましい。
　そして、前記増粘剤は、アクリル系ポリマー、カルボキシアルキルセルロース、キサンタンガム、グアーガム及びヒドロキシアルキルグアーガムからなる群から選択される１種以上であることがより好ましい。
　このような増粘剤を用いることで、保冷用組成物は、凍結の前後における色変化が大きく、かつ取り扱い性により優れたものとなる。 The thickener in the first embodiment may be at least one selected from the group consisting of acrylic polymer, carboxyalkyl cellulose, xanthan gum, guar gum, hydroxyalkyl guar gum, pectin, tamarind gum, carrageenan and alkylene glycol. preferable.
The thickener is more preferably one or more selected from the group consisting of acrylic polymers, carboxyalkyl cellulose, xanthan gum, guar gum and hydroxyalkyl guar gum.
By using such a thickener, the composition for cold preservation has a large color change before and after freezing and is excellent in handleability.
　第１実施形態における保冷用組成物が含有する増粘剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The thickener contained in the composition for cold insulation in the first embodiment may be only one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
　第１実施形態における凍結前及び凍結後の保冷用組成物中で、増粘剤の析出量は少ないほど好ましく、増粘剤の総量のうち析出している量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることがさらに好ましく、０質量％である（全量が析出していない）ことが特に好ましい。 In the composition for cold preservation before freezing and after freezing in the first embodiment, the amount of the thickener deposited is preferably as small as possible, and the amount deposited in the total amount of the thickener is 10% by mass or less. It is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 0% by mass (the total amount is not precipitated).
　第１実施形態における保冷用組成物の増粘剤の含有量は、０．１～１０質量％であることが好ましく、０．３～６質量％であることがより好ましく、０．６～３質量％であることが特に好ましい。 In the first embodiment, the content of the thickener in the composition for cold preservation is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and 0.6 to 3%. It is particularly preferable that the content is% by mass.
＜ｐＨ指示薬＞
　第１実施形態における前記ｐＨ指示薬（酸塩基指示薬）は、その発色の有無を反映させて保冷用組成物の色を決定する成分である。保冷用組成物は、ｐＨ指示薬を含有することにより、凍結の前後において色変化する。 <PH indicator>
The pH indicator (acid-base indicator) in the first embodiment is a component that determines the color of the composition for cold preservation by reflecting the presence or absence of color development. The composition for cold preservation changes a color before and after freezing by containing a pH indicator.
　第１実施形態における前記ｐＨ指示薬は、ｐＫａが４．９～８．０のものであれば、特に限定されない。
　なお、本実施形態におけるｐＨ指示薬のｐＫａは、特に断りのない限り、溶媒が水で温度が２５℃である場合の値を意味する。 The pH indicator in the first embodiment is not particularly limited as long as it has a pKa of 4.9 to 8.0.
In addition, unless otherwise indicated, pKa of the pH indicator in this embodiment means the value in case a solvent is water and temperature is 25 degreeC.
　ｐＨ指示薬は、その変色が観察されるｐＨ範囲、すなわち変色域を有している。ｐＨ指示薬は、溶液中で解離形と未解離形とに分かれて存在し、これらの間に解離平衡が成り立っており、解離形と未解離形とで呈する色が異なるものであるが、変色域外では、平衡は解離形か未解離形かのいずれか一方に著しく片寄っており、一方の色しかみられない。そして、変色域でｐＨ指示薬は、解離形と未解離形とが比較できる程度の量で混在しており、両方の色の混ざりがみられる（「化学大辞典縮刷版第３９刷、２００６年９月１５日」、共立出版株式会社」）。 The pH indicator has a pH range in which the color change is observed, that is, a color change range. A pH indicator exists in a solution in a dissociated form and an undissociated form, and a dissociation equilibrium is established between them. The dissociated form and the undissociated form have different colors. Then, the equilibrium is remarkably offset in either the dissociated form or the undissociated form, and only one color is seen. In the color change range, the pH indicator is mixed in an amount that can be compared between the dissociated form and the undissociated form, and a mixture of both colors is observed ("Chemical Dictionary Dictionary 39th Edition, 2006 9"). May 15 ", Kyoritsu Publishing Co., Ltd.)).
　表１に主なｐＨ指示薬の例を示す。表１には、ｐＨ指示薬と共に、その変色域及び色変化をあわせて記載している。なお、表１中の「色変化（低ｐＨ→高ｐＨ）」とは、ｐＨ指示薬が含有されている液体のｐＨが、特定の値からこれよりも高い値へ変化した際に、ｐＨ指示薬が変色域内で示す色変化を意味し、例えば、「赤→黄」とは、前記液体のｐＨが高くなる過程で、ｐＨ指示薬が前記液体を赤色から黄色に色変化させることを意味する。 Table 1 shows examples of main pH indicators. Table 1 shows the color change area and color change together with the pH indicator. “Color change (low pH → high pH)” in Table 1 means that the pH indicator changes when the pH of the liquid containing the pH indicator changes from a specific value to a higher value. For example, “red → yellow” means that the pH indicator changes the color of the liquid from red to yellow in the process of increasing the pH of the liquid.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　第１実施形態におけるｐＨ指示薬は、例えば、その変色域（ｐＨ）が３．０～１０．５の範囲内にあるものが好ましく、４．０～９．５の範囲内にあるものがより好ましく、４．５～９．０の範囲内にあるものが特に好ましい。 The pH indicator in the first embodiment, for example, preferably has a color change range (pH) in the range of 3.0 to 10.5, more preferably in the range of 4.0 to 9.5. Particularly preferred are those in the range of 4.5 to 9.0.
　第１実施形態における保冷用組成物が含有するｐＨ指示薬は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。ただし、通常はｐＨ指示薬を１種のみ含有することが好ましい。 1 type may be sufficient as the pH indicator which the composition for cold preservation in 1st Embodiment contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily. However, it is usually preferable to contain only one kind of pH indicator.
　第１実施形態における保冷用組成物のｐＨ指示薬の含有量は、保冷用組成物の目的とする色変化が達成される限り特に限定されないが、１～３０ｐｐｍであることが好ましく、５～２０ｐｐｍであることがより好ましい。 The content of the pH indicator in the cold-retaining composition in the first embodiment is not particularly limited as long as the intended color change of the cold-retaining composition is achieved, but is preferably 1 to 30 ppm, and is preferably 5 to 20 ppm. More preferably.
＜その他の成分＞
　第１実施形態における保冷用組成物は、水、無機塩、増粘剤及びｐＨ指示薬以外に、本発明の効果を損なわない範囲内において、これらに該当しないその他の成分を含有していてもよい。前記その他の成分としては、水以外の溶媒；防腐剤、界面活性剤等の公知の各種添加剤等が挙げられる。
　第１実施形態における保冷用組成物が含有する前記その他の成分は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 <Other ingredients>
The composition for cold preservation in 1st Embodiment may contain the other component which does not correspond to these in the range which does not impair the effect of this invention other than water, an inorganic salt, a thickener, and a pH indicator. . Examples of the other components include solvents other than water; various known additives such as preservatives and surfactants.
The said other component which the composition for cold preservation in 1st Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.
（溶媒）
　第１実施形態における前記溶媒は、前記無機塩、増粘剤及びｐＨ指示薬を溶解可能なものが好ましく、このようなものとしては、例えば、アルコール等が挙げられる。 (solvent)
The solvent in the first embodiment is preferably one that can dissolve the inorganic salt, thickener, and pH indicator, and examples of such a solvent include alcohol.
　水及び前記溶媒は、保冷剤の一成分として機能する成分であり、前記無機塩と共に、主にこれらの種類及び量により、保冷用組成物の凍結温度が決定される。
　第１実施形態での保冷用組成物において、水及び前記溶媒の総含有量に対する前記溶媒の含有量の割合は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることが特に好ましい。 Water and the solvent are components that function as one component of a cryogen, and together with the inorganic salt, the freezing temperature of the cryopreservation composition is determined mainly by the type and amount thereof.
In the composition for cold preservation in the first embodiment, the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less. 2% by mass or less is particularly preferable.
（防腐剤）
　第１実施形態における前記防腐剤としては、例えば、食品保存料、酸化防止剤等が挙げられ、より具体的には、ナトリウムピリチオン、パラベン（パラオキシ安息香酸エステル）、プロタミン、有機窒素硫黄系化合物等が挙げられる。 (Preservative)
Examples of the preservative in the first embodiment include food preservatives, antioxidants, and the like. More specifically, sodium pyrithione, paraben (paraoxybenzoic acid ester), protamine, organic nitrogen sulfur-based compound, and the like. Is mentioned.
　第１実施形態における保冷用組成物の防腐剤の含有量は、特に限定されないが、０．０２～０．５質量％であることが好ましく、０．０４～０．２質量％であることがより好ましい。 The content of the preservative in the composition for cold preservation in the first embodiment is not particularly limited, but is preferably 0.02 to 0.5% by mass, and preferably 0.04 to 0.2% by mass. More preferred.
（界面活性剤）
　第１実施形態における前記界面活性剤としては、公知のものが挙げられ、例えば、ドデシル硫酸ナトリウム等のアルキル硫酸塩；デカン酸ナトリウム等のアルキルカルボン酸塩；Ｎ－イソプロピルアクリルアミド等のＮ－アルキルアクリルアミド；ポリオキシエチレンオクチルドデシルエーテル等のポリオキシエチレンジアルキルエーテル；ポリオキシエチレンラウリルエーテル等のポリオキシエチレンモノアルキルエーテル；ポリオキシエチレンオレイルエーテル等のポリオキシエチレンモノアルケニルエーテル等が挙げられる。 (Surfactant)
Examples of the surfactant in the first embodiment include known ones such as alkyl sulfates such as sodium dodecyl sulfate; alkyl carboxylates such as sodium decanoate; N-alkyl acrylamides such as N-isopropylacrylamide. Polyoxyethylene dialkyl ethers such as polyoxyethylene octyldodecyl ether; polyoxyethylene monoalkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene monoalkenyl ethers such as polyoxyethylene oleyl ether;
　第１実施形態における保冷用組成物は、水及び前記溶媒以外の成分（前記無機塩、増粘剤、ｐＨ指示薬、及び前記溶媒以外のその他の成分）の総含有量に対する、前記無機塩、増粘剤及びｐＨ指示薬の総含有量の割合が、９０質量％以上であることが好ましく、９３質量％以上であることがより好ましく、９６質量％以上であることがさらに好ましく、９８質量％以上であることが特に好ましく、１００質量%であってもよい。前記総含有量の割合が前記下限値以上であることで、保冷用組成物は凍結の前後においてより大きく色変化する。 The composition for cold preservation in 1st Embodiment is the said inorganic salt, increase with respect to the total content of components other than water and the said solvent (The said inorganic salt, a thickener, a pH indicator, and other components other than the said solvent). The ratio of the total content of the adhesive and the pH indicator is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 96% by mass or more, and 98% by mass or more. It is particularly preferable that it may be 100% by mass. When the ratio of the total content is equal to or higher than the lower limit value, the color of the cold-retaining composition changes more greatly before and after freezing.
　第１実施形態における保冷用組成物は、リン酸塩、リン酸二水素塩及び水以外の含有成分をすべて除去した場合のｐＨ（α１）が、前記ｐＨ指示薬のｐＫａに対して、下記式（ｉ）で表される関係を満たす。
　ｐＨ指示薬のｐＫａ≦ｐＨ（α１）≦ｐＨ指示薬のｐＫａ＋１．８　・・・・（ｉ）
　ｐＨ（α１）は、第１実施形態における保冷用組成物が含有する量と同じ量のリン酸塩、リン酸二水素塩及び水のみを混合して得られた混合液（例えば、リン酸塩及びリン酸二水素塩を含有する水溶液）のｐＨに相当する。ｐＨ（α１）は、前記保冷用組成物で用いるリン酸塩及びリン酸二水素塩の混合物について、その酸性度の指標となるものである。 In the composition for cold preservation in the first embodiment, the pH (α1) when all the components other than phosphate, dihydrogen phosphate and water are removed is expressed by the following formula (pKa) of the pH indicator: The relationship represented by i) is satisfied.
pKa of pH indicator ≦ pH (α1) ≦ pKa of pH indicator + 1.8 (i)
pH (α1) is a mixed solution (for example, phosphate) obtained by mixing only the same amount of phosphate, dihydrogen phosphate and water as the amount contained in the composition for cold preservation in the first embodiment. And the pH of an aqueous solution containing dihydrogen phosphate). The pH (α1) serves as an index of the acidity of the mixture of phosphate and dihydrogen phosphate used in the cold insulation composition.
　ｐＨ（α１）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記混合液の温度が２５℃であるときのｐＨであることがより好ましい。 The pH (α1) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the temperature of the mixed solution is 25 ° C.
　ｐＨ（α１）は、前記式（ｉ）の関係を満たした上で、さらに、５．０～１０．６であることが好ましく、５．３～１０．３であることがより好ましく、５．６～１０．０であることが特に好ましい。 The pH (α1) preferably further satisfies 5.0 to 10.6, more preferably 5.3 to 10.3, while satisfying the relationship of the above formula (i). Particularly preferred is 6 to 10.0.
　第１実施形態における保冷用組成物のｐＨは、４．６～８．８であることが好ましく、４．９～８．５であることがより好ましく、５．１～８．３であることが特に好ましい。
　第１実施形態における保冷用組成物は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度で前記数値範囲のｐＨを示すことが好ましく、前記保冷用組成物の温度が２５℃であるときに前記数値範囲のｐＨを示すことがより好ましい。
　なお、本実施形態において、保冷用組成物についての単なる「ｐＨ」との記載は、特に断りのない限り、保冷用組成物自体のｐＨを意味するものとする。 The pH of the composition for cold preservation in the first embodiment is preferably 4.6 to 8.8, more preferably 4.9 to 8.5, and 5.1 to 8.3. Is particularly preferred.
The composition for cold preservation in the first embodiment preferably exhibits a pH in the numerical range at a temperature at which the pH indicator is dissolved in the composition for cold preservation, and the temperature of the composition for cold insulation is 25 ° C. Sometimes it is more preferred to exhibit a pH in the numerical range.
In addition, in this embodiment, description with mere "pH" about the composition for cold preservation shall mean the pH of the composition for cold preservation itself unless there is particular notice.
　第１実施形態における保冷用組成物は、前記無機塩及び水以外の含有成分をすべて水で置換した場合のｐＨ（α２）が、４．４～８．７であることが好ましく、４．９～８．２であることがより好ましい。
　ｐＨ（α２）は、前記保冷用組成物での含有量（質量％）と同じ含有量（質量％）で前記無機塩のみを含有する無機塩含有水（例えば、無機塩水溶液）のｐＨに相当する。ｐＨ（α２）は、前記保冷用組成物で用いる無機塩の酸性度の指標となるものである。
　ｐＨ（α２）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記無機塩含有水が２５℃であるときのｐＨであることがより好ましい。 The composition for cold preservation in the first embodiment preferably has a pH (α2) of 4.4 to 8.7 when all the components other than the inorganic salt and water are replaced with water. More preferably, it is ˜8.2.
The pH (α2) corresponds to the pH of an inorganic salt-containing water (for example, an inorganic salt aqueous solution) containing only the inorganic salt at the same content (mass%) as the content (mass%) in the composition for cold preservation. To do. The pH (α2) serves as an index of the acidity of the inorganic salt used in the cold insulation composition.
The pH (α2) is preferably the pH at the temperature at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the inorganic salt-containing water is 25 ° C.
　第１実施形態における保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が、６．０～８．５であることが好ましく、６．０～８．３であることがより好ましく、例えば、６．０～８．０であってもよいし、６．５～７．５であってもよい。
　ｐＨ（α３）は、前記保冷用組成物での含有量（質量％）と同じ含有量（質量％）で前記増粘剤のみを含有する増粘剤含有水（例えば、増粘剤水溶液）のｐＨに相当する。ｐＨ（α３）は、前記保冷用組成物で用いる増粘剤の酸性度の指標となるものである。
　ｐＨ（α３）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記増粘剤含有水が２５℃であるときのｐＨであることがより好ましい。 The composition for cold preservation in the first embodiment preferably has a pH (α3) of 6.0 to 8.5 when all the components other than the thickener and water are replaced with water. It is more preferably from 0 to 8.3, for example, from 6.0 to 8.0, or from 6.5 to 7.5.
pH (α3) is the same as the content (mass%) in the cold insulation composition (mass%) of the thickener-containing water (eg, thickener aqueous solution) containing only the thickener. Corresponds to pH. The pH (α3) serves as an index of the acidity of the thickener used in the cold insulation composition.
The pH (α3) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the thickener-containing water is 25 ° C. .
　第１実施形態における保冷用組成物は、水、前記無機塩、増粘剤、ｐＨ指示薬、及び必要に応じて前記その他の成分を配合することで得られる。
　各成分の配合方法は特に限定されず、保冷用組成物の凍結温度よりも高い温度において、各成分が均一に溶解又は分散するように、任意に調節できる。
　例えば、各成分の配合時には、すべての成分を添加してからこれらを混合してもよいし、一部の成分を順次添加しながら混合してもよく、すべての成分を順次添加しながら混合してもよい。
　混合方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサー、三本ロール、ニーダー又はビーズミル等を使用して混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。 The composition for cold preservation in 1st Embodiment is obtained by mix | blending water, the said inorganic salt, a thickener, a pH indicator, and the said other component as needed.
The blending method of each component is not particularly limited, and can be arbitrarily adjusted so that each component is uniformly dissolved or dispersed at a temperature higher than the freezing temperature of the composition for cold preservation.
For example, when blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, and all components may be mixed while being added sequentially. May be.
The mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.
　本発明の第１実施形態に係る保冷具は、前記保冷用組成物を備えたものであり、例えば、液状物を封入可能な容器状、袋状等の保持手段によって、保冷用組成物を保持することで構成される。 The cold insulation tool according to the first embodiment of the present invention is provided with the cold insulation composition. For example, the cold insulation composition is held by a holding means such as a container or bag that can enclose a liquid material. It is composed by doing.
　前記保持手段の材質は、保持された保冷用組成物の色変化（変色）が視認可能な程度に透明性を有していれば、特に限定されない。
　好ましい保持手段の材質としては、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン；ポリアミド；ポリエステル等の合成樹脂等が挙げられる。ポリエチレンとしては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等が挙げられる。 The material of the holding means is not particularly limited as long as the holding means has transparency to such an extent that the color change (discoloration) of the held cold insulating composition is visible.
Examples of preferable holding means include polyolefins such as polyethylene and polypropylene; polyamides; synthetic resins such as polyesters and the like. Examples of polyethylene include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE).
　前記保持手段の材質や大きさは、例えば、保持手段の形態、保冷用組成物の保持量、又は凍結の前後における保冷用組成物の色変化の仕方等を考慮して、選択すればよい。
　例えば、袋状の保持手段の場合には、好ましい保持手段の材質の一例としては、低密度ポリエチレンが挙げられる。また、容器状の保持手段の場合には、好ましい保持手段の材質の一例としては、高密度ポリエチレンが挙げられる。
　例えば、袋状の保持手段は、これを小さいものとして用いる場合、すなわち保冷用組成物の保持量が比較的少ない場合に好ましい。また、容器状の保持手段は、これを大きいものとして用いる場合、すなわち保冷用組成物の保持量が比較的多い場合に好ましい。
　ただし、ここに示す保持手段の材質や大きさの選択方法は一例に過ぎない。 The material and size of the holding means may be selected in consideration of, for example, the shape of the holding means, the amount of the cold-retaining composition held, or how the color of the cold-retaining composition changes before and after freezing.
For example, in the case of a bag-shaped holding means, an example of a preferable material of the holding means is low density polyethylene. In the case of a container-shaped holding means, an example of a preferable material for the holding means is high-density polyethylene.
For example, the bag-like holding means is preferable when it is used as a small one, that is, when the amount of the cold-retaining composition is relatively small. The container-like holding means is preferable when it is used as a large one, that is, when the amount of the cold-retaining composition is relatively large.
However, the method for selecting the material and size of the holding means shown here is merely an example.
　前記保持手段の材質は、耐低温脆性、耐水性及び耐薬品性等に優れる点においては、ポリオレフィンであることが好ましく、さらに成形が容易で、高い強度を有する点においては、高密度ポリエチレンであることがより好ましい。 The material of the holding means is preferably polyolefin in terms of excellent low temperature brittleness resistance, water resistance and chemical resistance, and is high density polyethylene in terms of easy molding and high strength. It is more preferable.
　前記保持手段中のフィルム状又はシート状等の扁平部位の厚さは、特に限定されないが、５～２００μｍであることが好ましい。 The thickness of the flat part such as a film or sheet in the holding means is not particularly limited, but is preferably 5 to 200 μm.
　前記扁平部位は、単層からなるものでもよいし、２層以上の複数層からなるものでもよい。前記扁平部位が複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよい。すなわち、すべての層が同一であってもよいし、すべての層が異なっていてもよく、一部の層のみが同一であってもよい。そして、複数層が互いに異なる場合、これら複数層の組み合わせは特に限定されない。ここで、複数層が互いに異なるとは、各層の材質及び厚さの少なくとも一方が互いに異なることを意味する。
　前記扁平部位が複数層からなる場合には、各層の合計の厚さが、上記の好ましい扁平部位の厚さとなるようにするとよい。 The flat part may be composed of a single layer or may be composed of two or more layers. When the flat portion is composed of a plurality of layers, the plurality of layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be the same. And when several layers differ from each other, the combination of these several layers is not specifically limited. Here, the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
When the flat part is composed of a plurality of layers, the total thickness of each layer is preferably the thickness of the preferred flat part.
　第１実施形態における保冷用組成物は、凍結の前後において大きく色変化するために、凍結の有無を容易に視認可能である。そして、保冷用組成物のこの色変化が、保冷具の外側から視認可能となっている。これにより保冷具は、所望の温度にまで十分に冷却されているか否かが容易に視認可能となっている。
　また、前記保冷用組成物は、凍結及び解凍を繰り返すなど、冷却及び昇温を繰り返しても、効果が損なわれることがない。従って、前記保冷用組成物を備えた保冷具は、繰り返し利用にも適している。 Since the composition for cold preservation in the first embodiment largely changes in color before and after freezing, the presence or absence of freezing can be easily visually confirmed. And this color change of the composition for cold insulation is visible from the outer side of a cold insulator. Thereby, it is possible to easily visually check whether the cold insulator is sufficiently cooled to a desired temperature.
The effect of the cold-retaining composition is not impaired even when the cooling and heating are repeated, such as repeated freezing and thawing. Therefore, the cold insulator provided with the cold-retaining composition is also suitable for repeated use.
＜＜第２実施形態＞＞
　本発明の第２実施形態に係る保冷具は、水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸一水素塩と、を含有し、前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸一水素塩の合計含有量の割合が、５～１００質量％であり、前記保冷用組成物において、水、前記無機塩及び増粘剤の総含有量に対する、リン酸一水素塩の含有量の割合が、０．２～５．０質量％であり、前記ｐＨ指示薬のｐＫａが４．９～８．０である。 << Second Embodiment >>
The cold insulation device according to the second embodiment of the present invention is a cold insulation device provided with a cold insulation composition containing water, an inorganic salt, a thickener, and a pH indicator, wherein the cold insulation composition is the inorganic salt. The aqueous solution contains an acidic inorganic salt that exhibits acidity and monohydrogen phosphate, and in the composition for cold preservation, the acidic inorganic salt and monobasic phosphate with respect to the total content of the inorganic salt The ratio of the total content of hydrogen salt is 5 to 100% by mass, and the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt and the thickener in the composition for cold preservation Is 0.2 to 5.0% by mass, and the pKa of the pH indicator is 4.9 to 8.0.
　前記保冷具の保冷用組成物の色は、保冷用組成物の凍結の前後において大きく変化する。ここで、保冷用組成物の色は、、ｐＨ指示薬の発色の有無が反映されたものである。そのため、前記保冷具は、冷却状態が目的とする状態（対象物を十分に冷却できる状態）にあるか容易に視認可能となっている。そして、凍結の前後における保冷用組成物の色は、前記無機塩、増粘剤等のｐＨ指示薬以外の含有成分自体の色を主として反映したものではない。 The color of the cold insulation composition of the cold insulation tool varies greatly before and after freezing of the cold insulation composition. Here, the color of the composition for cold preservation reflects the presence or absence of color development of the pH indicator. Therefore, the cold insulator can be easily visually confirmed whether the cooling state is in a target state (a state in which the object can be sufficiently cooled). And the color of the composition for cold preservation before and after freezing does not mainly reflect the color of components other than pH indicators, such as the said inorganic salt and a thickener.
　第２実施形態における保冷用組成物は、その酸性度に影響を与える成分として、無機塩及び増粘剤を含有する。そして、前記保冷用組成物においては、前記無機塩として、酸性の無機塩及びリン酸一水素塩という特定の組み合わせを選択し、これら無機塩の含有量を限定し、リン酸一水素塩については、水、無機塩及び増粘剤の総含有量に対する含有量の割合も限定し、さらにこれら無機塩及び増粘剤に対して、ｐＫａが特定範囲にあるｐＨ指示薬を組み合わせて用いている。このような構成を有する前記保冷用組成物は、ｐＨ指示薬の発色の変化又は有無に依存して、顕著に大きく色変化する。 The composition for cold preservation in the second embodiment contains an inorganic salt and a thickener as components that affect the acidity. And in the composition for cold preservation, as the inorganic salt, a specific combination of an acidic inorganic salt and a monohydrogen phosphate is selected, the content of these inorganic salts is limited, and the monohydrogen phosphate is The ratio of the content to the total content of water, inorganic salt, and thickener is also limited, and a pH indicator having a pKa in a specific range is used in combination with these inorganic salt and thickener. The cold-retaining composition having such a configuration changes color remarkably greatly depending on the change in color presence or absence of the pH indicator.
＜無機塩＞
　第２実施形態における前記無機塩は、保冷剤の一成分として機能し、主にその種類及び量により、保冷用組成物の凍結温度が決定される。
　また、前記無機塩は、前記ｐＨ指示薬に該当しない成分であり、保冷用組成物の凍結時に、結晶又はアモルファス（非晶質）として析出し、その析出の有無によって、保冷用組成物の色変化に関与する。 <Inorganic salt>
The said inorganic salt in 2nd Embodiment functions as one component of a cryoprotectant, and the freezing temperature of the composition for cold preservation is mainly determined by the kind and quantity.
The inorganic salt is a component that does not correspond to the pH indicator, and precipitates as crystals or amorphous (amorphous) at the time of freezing of the cold insulation composition, and the color change of the cold insulation composition depends on the presence or absence of the precipitation. Involved in.
　第２実施形態における前記保冷用組成物は、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸一水素塩と、を含有する。 The said composition for cold preservation in 2nd Embodiment contains the acidic inorganic salt in which the aqueous solution shows acidity, and monohydrogen phosphate as said inorganic salt.
［酸性の無機塩］
　第２実施形態における前記酸性の無機塩は、特に限定されず、目的に応じて適宜選択でき、非水和物であってもよいし、水和物であってもよい。
　第２実施形態における酸性の無機塩としては、例えば、第１実施形態における前記酸性の無機塩と同じもの、すなわち、リン酸二水素塩とリン酸二水素塩以外の無機塩と、が挙げられる。 [Acid inorganic salt]
The acidic inorganic salt in the second embodiment is not particularly limited and can be appropriately selected depending on the purpose, and may be a non-hydrate or a hydrate.
As an acidic inorganic salt in 2nd Embodiment, the same thing as the said acidic inorganic salt in 1st Embodiment, ie, inorganic salts other than dihydrogen phosphate and dihydrogen phosphate, is mentioned, for example. .
　第２実施形態における保冷用組成物が含有する前記酸性の無機塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The acidic inorganic salt contained in the composition for cold insulation in the second embodiment may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. .
［リン酸一水素塩］
　第２実施形態における前記リン酸一水素塩は、リン酸（Ｈ３ＰＯ４）中の２個の水素イオンがカチオンで置換されてなるものであり、非水和物であってもよいし、水和物であってもよい。
　前記リン酸一水素塩は、通常、その水溶液が塩基性を示す塩基性の塩である。 [Monophosphate]
The monohydrogen phosphate in the second embodiment is obtained by replacing two hydrogen ions in phosphoric acid (H 3 PO 4 ) with a cation, and may be a non-hydrate, Hydrates may also be used.
The monohydrogen phosphate is generally a basic salt whose aqueous solution shows basicity.
　第２実施形態におけるリン酸一水素塩としては、例えば、リン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）、リン酸水素二カリウム（Ｋ２ＨＰＯ４）、リン酸水素カルシウム（ＣａＨＰＯ４）等のリン酸一水素金属塩；リン酸水素二アンモニウム（（ＮＨ４）２ＨＰＯ４）等のリン酸一水素非金属塩等が挙げられる。 Examples of the monohydrogen phosphate in the second embodiment include phosphorus such as disodium hydrogen phosphate (Na 2 HPO 4 ), dipotassium hydrogen phosphate (K 2 HPO 4 ), and calcium hydrogen phosphate (CaHPO 4 ). Examples thereof include metal monohydrogen phosphate; non-metal monohydrogen phosphate such as diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ).
　第２実施形態における保冷用組成物が含有するリン酸一水素塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 1 type of phosphoric acid monohydrogen salt which the composition for cold preservation in 2nd Embodiment contains may be one, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
［その他の無機塩］
　第２実施形態における保冷用組成物は、前記無機塩として、前記酸性の無機塩及びリン酸一水素塩以外に、これらのいずれにも該当しないその他の無機塩を含有していてもよい。
　前記その他の無機塩は、非水和物であってもよいし、水和物であってもよい。 [Other inorganic salts]
The composition for cold preservation in 2nd Embodiment may contain the other inorganic salt which does not correspond to any of these other than the said acidic inorganic salt and phosphoric acid monohydrogen salt as said inorganic salt.
The other inorganic salts may be non-hydrates or hydrates.
　第２実施形態における前記その他の無機塩は、本発明の効果を損なわない限り特に限定されないが、例えば、その水溶液が中性を示す中性の無機塩、その水溶液が塩基性を示すリン酸一水素塩以外の無機塩等が挙げられる。 Although the said other inorganic salt in 2nd Embodiment is not specifically limited unless the effect of this invention is impaired, For example, the neutral inorganic salt in which the aqueous solution shows neutrality, The phosphoric acid one in which the aqueous solution shows basicity Examples include inorganic salts other than hydrogen salts.
　前記中性の無機塩としては、例えば、第１実施形態における前記中性の無機塩と同じものが挙げられ、塩化ナトリウム、塩化カリウム又は硫酸ナトリウムであることが好ましい。 Examples of the neutral inorganic salt include the same neutral inorganic salt as in the first embodiment, and sodium chloride, potassium chloride, or sodium sulfate is preferable.
　前記リン酸一水素塩以外の塩基性の無機塩は、リン酸塩以外の無機塩であることが好ましく、例えば、第１実施形態における前記リン酸塩以外の塩基性の無機塩と同じものが挙げられ、炭酸ナトリウム又は炭酸カリウムであることが好ましい。 The basic inorganic salt other than the phosphate monobasic salt is preferably an inorganic salt other than a phosphate, and for example, the same basic inorganic salt other than the phosphate in the first embodiment may be used. And is preferably sodium carbonate or potassium carbonate.
　第２実施形態における保冷用組成物が含有する前記その他の無機塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The said other inorganic salt which the composition for cold preservation in 2nd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
　第２実施形態における保冷用組成物で好ましいものとしては、前記酸性の無機塩であるリン酸二水素塩と、中性の無機塩と、を含有するものが挙げられる。このような保冷用組成物は、凍結の前後における色変化の完了に要する時間がより短く、より好ましい性状を有する。 Preferred examples of the cold-retaining composition in the second embodiment include those containing the dihydrogen phosphate salt, which is the acidic inorganic salt, and a neutral inorganic salt. Such a cold-retaining composition has a shorter time required for completion of the color change before and after freezing and has more preferable properties.
　第２実施形態における保冷用組成物が、リン酸二水素塩及び中性の無機塩を含有する場合、前記中性の無機塩は、塩化ナトリウム又は塩化カリウムであることが好ましい。このような中性の無機塩を併用することで、第２実施形態における保冷用組成物は、凍結の前後において、より短時間で色変化が完了する。 When the composition for cold preservation in the second embodiment contains a dihydrogen phosphate salt and a neutral inorganic salt, the neutral inorganic salt is preferably sodium chloride or potassium chloride. By using such a neutral inorganic salt together, the color change of the composition for cold preservation in the second embodiment is completed in a shorter time before and after freezing.
　第２実施形態における保冷用組成物が、リン酸二水素塩及び中性の無機塩を含有する場合、無機塩の総含有量に対する、中性の無機塩の含有量の割合は、４０～６０質量％であることが好ましく、４３～５７質量％であることがより好ましく、４６～５４質量％であることが特に好ましい。前記割合がこのような範囲であることで、第２実施形態における保冷用組成物は、凍結の前後において、より短時間で色変化が完了し、かつより大きく色変化する。 When the composition for cold preservation in the second embodiment contains dihydrogen phosphate and neutral inorganic salt, the ratio of the content of neutral inorganic salt to the total content of inorganic salt is 40 to 60. The content is preferably mass%, more preferably 43 to 57 mass%, particularly preferably 46 to 54 mass%. When the ratio is in such a range, the composition for cold preservation in the second embodiment completes a color change in a shorter time and undergoes a greater color change before and after freezing.
　第２実施形態における保冷用組成物が、リン酸二水素塩及び中性の無機塩を含有する場合、リン酸一水素塩の含有量（質量）に対する、リン酸二水素塩の含有量（質量）の比率（［保冷用組成物のリン酸二水素塩の含有量（質量）］／［保冷用組成物のリン酸一水素塩の含有量（質量）］）は、０．０４～２であることが好ましく、０．０４～１．６であることがより好ましく、０．０４～１．４であることが特に好ましい。前記比率がこのような範囲であることで、第２実施形態における保冷用組成物は、凍結の前後において、より短時間で色変化が完了する。
　さらに、第２実施形態における保冷用組成物が、凍結の前後において、より大きく色変化することから、前記比率は、０．０４～１．２であることが好ましく、０．０７～０．８であることがより好ましく、０．１～０．６であることが特に好ましい。 When the composition for cold preservation in 2nd Embodiment contains phosphoric acid dihydrogen salt and neutral inorganic salt, content (mass) of dihydrogen phosphate with respect to content (mass) of monohydrogen phosphate ) Ratio ([content of dihydrogen phosphate in the composition for cold insulation (mass)] / [content of monohydrogen phosphate in the composition for cold insulation (mass)]) is 0.04 to 2 It is preferably 0.04 to 1.6, more preferably 0.04 to 1.4. When the ratio is in such a range, the color change of the composition for cold insulation in the second embodiment is completed in a shorter time before and after freezing.
Furthermore, since the color-retaining composition in the second embodiment undergoes a greater color change before and after freezing, the ratio is preferably 0.04 to 1.2, preferably 0.07 to 0.8. Is more preferable, and 0.1 to 0.6 is particularly preferable.
　第２実施形態での保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸一水素塩の合計含有量の割合は、５～１００質量％であり、５．５～１００質量％であることが好ましく、６～１００質量％であることがより好ましい。前記割合が前記下限値以上であることで、保冷用組成物は、凍結の前後における色変化が大きくなる。
　このような数値範囲の中で、前記割合の下限値としては、例えば、１０質量％、２０質量％、３０質量％、４０質量％、４５質量％等が選択できるが、これらに限定されない。また、このような数値範囲の中で、前記割合の上限値としては、例えば、９０質量％、８０質量％、７５質量％、７０質量％、６５質量％等が選択できるが、これらに限定されない。 In the composition for cold preservation in the second embodiment, the ratio of the total content of the acidic inorganic salt and monohydrogen phosphate to the total content of the inorganic salt is 5 to 100% by mass. The content is preferably 5 to 100% by mass, more preferably 6 to 100% by mass. When the said ratio is more than the said lower limit, the composition for cold preservation becomes large in the color change before and behind freezing.
In such a numerical range, as the lower limit of the ratio, for example, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 45% by mass and the like can be selected, but not limited thereto. Further, in such a numerical range, as the upper limit value of the ratio, for example, 90% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass and the like can be selected, but not limited thereto. .
　第２実施形態における凍結前、好ましくは０℃以上の保冷用組成物中で、前記無機塩の溶解量は多いほど好ましく、前記無機塩の総量のうち溶解している量が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがさらに好ましく、１００質量％（全量）であってもよい。
　また、第２実施形態における凍結後の保冷用組成物中で、前記無機塩の析出量は多いほど好ましく、前記無機塩の総量のうち析出している量が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがさらに好ましく、１００質量％（全量）であってもよい。 Before freezing in the second embodiment, preferably in the cold-retaining composition at 0 ° C. or higher, the amount of the inorganic salt dissolved is preferably as large as possible, and the amount dissolved in the total amount of the inorganic salt is 90% by mass or more. Preferably, it is 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
Moreover, in the composition for cold preservation after freezing in 2nd Embodiment, it is so preferable that there is much precipitation amount of the said inorganic salt, and it is preferable that the amount which has precipitated among the total amount of the said inorganic salt is 90 mass% or more. 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
　第２実施形態における保冷用組成物の無機塩の総含有量は、５～３５質量％であることが好ましく、５～３０質量％であることがより好ましく、１０～３０質量％であることがさらに好ましく、例えば、１５～２５質量％であってもよい。 In the second embodiment, the total content of the inorganic salt of the composition for cold insulation is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, and 10 to 30% by mass. More preferably, for example, it may be 15 to 25% by mass.
＜増粘剤＞
　第２実施形態における前記増粘剤は、保冷用組成物の粘度を増大させ、前記ｐＨ指示薬に該当しない成分である。第２実施形態における前記増粘剤は、保冷用組成物の凍結時に析出しないものが好ましい。なお、本明細書において「増粘剤が保冷用組成物の凍結時に析出しない」とは、第１実施形態において、先に説明したとおりである。 <Thickener>
The said thickener in 2nd Embodiment is a component which increases the viscosity of the composition for cold preservation, and does not correspond to the said pH indicator. The thickener in the second embodiment is preferably one that does not precipitate when the composition for cold preservation is frozen. In the present specification, “the thickener does not precipitate when the composition for cold preservation is frozen” is as described above in the first embodiment.
　第２実施形態における前記増粘剤としては、例えば、第１実施形態における増粘剤と同じものが挙げられる。
　第１実施形態の場合と同様に、第２実施形態における前記増粘剤は、アクリル系ポリマー、カルボキシアルキルセルロース、キサンタンガム、グアーガム、ヒドロキシアルキルグアーガム、ペクチン、タマリンドガム、カラギーナン及びアルキレングリコールからなる群から選択される１種以上であることが好ましい。
　そして、前記増粘剤は、アクリル系ポリマー、カルボキシアルキルセルロース、キサンタンガム、グアーガム及びヒドロキシアルキルグアーガムからなる群から選択される１種以上であることがより好ましい。
　このような増粘剤を用いることで、保冷用組成物は、凍結の前後における色変化が大きく、かつ取り扱い性により優れたものとなる。 As said thickener in 2nd Embodiment, the same thing as the thickener in 1st Embodiment is mentioned, for example.
As in the case of the first embodiment, the thickener in the second embodiment is selected from the group consisting of acrylic polymer, carboxyalkyl cellulose, xanthan gum, guar gum, hydroxyalkyl guar gum, pectin, tamarind gum, carrageenan and alkylene glycol. It is preferable that it is 1 or more types selected.
The thickener is more preferably one or more selected from the group consisting of acrylic polymers, carboxyalkyl cellulose, xanthan gum, guar gum and hydroxyalkyl guar gum.
By using such a thickener, the composition for cold preservation has a large color change before and after freezing and is excellent in handleability.
　第２実施形態における保冷用組成物が含有する増粘剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The thickener contained in the composition for cold insulation in the second embodiment may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　第２実施形態における凍結前及び凍結後の保冷用組成物中で、増粘剤の析出量は少ないほど好ましく、増粘剤の総量のうち析出している量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることがさらに好ましく、０質量％である（全量が析出していない）ことが特に好ましい。 In the composition for cold preservation before freezing and after freezing in the second embodiment, the amount of the thickener deposited is preferably as small as possible, and the amount deposited in the total amount of the thickener is 10% by mass or less. It is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 0% by mass (the total amount is not precipitated).
　第２実施形態における保冷用組成物の増粘剤の含有量は、０．１～１０質量％であることが好ましく、０．３～６質量％であることがより好ましく、０．６～３質量％であることが特に好ましい。 In the second embodiment, the content of the thickener in the composition for cold preservation is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and 0.6 to 3%. It is particularly preferable that the content is% by mass.
　第２実施形態での保冷用組成物において、水、前記無機塩及び増粘剤の総含有量に対する、リン酸一水素塩の含有量の割合は、０．２～５．０質量％であり、０．２３～４．９質量％であることが好ましく、０．２６～４．８質量％であることがより好ましい。前記割合がこのような範囲であることで、保冷用組成物は、凍結の前後における色変化が大きくなる。 In the composition for cold preservation in the second embodiment, the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt, and the thickener is 0.2 to 5.0% by mass. 0.23 to 4.9% by mass, more preferably 0.26 to 4.8% by mass. When the ratio is in such a range, the color change before and after freezing increases in the composition for cold preservation.
＜ｐＨ指示薬＞
　第２実施形態における前記ｐＨ指示薬（酸塩基指示薬）は、その発色の有無を反映させて保冷用組成物の色を決定する成分である。保冷用組成物は、ｐＨ指示薬を含有することにより、凍結の前後において色変化する。 <PH indicator>
The pH indicator (acid-base indicator) in the second embodiment is a component that determines the color of the composition for cold preservation by reflecting the presence or absence of color development. The composition for cold preservation changes a color before and after freezing by containing a pH indicator.
　第２実施形態における前記ｐＨ指示薬は、ｐＫａが４．９～８．０のものであれば、特に限定されない。
　なお、本実施形態におけるｐＨ指示薬のｐＫａは、特に断りのない限り、溶媒が水で温度が２５℃である場合の値を意味する。
　第２実施形態における前記ｐＨ指示薬としては、例えば、第１実施形態におけるｐＨ指示薬と同じものが挙げられる。 The pH indicator in the second embodiment is not particularly limited as long as it has a pKa of 4.9 to 8.0.
In addition, unless otherwise indicated, pKa of the pH indicator in this embodiment means the value in case a solvent is water and temperature is 25 degreeC.
As said pH indicator in 2nd Embodiment, the same thing as the pH indicator in 1st Embodiment is mentioned, for example.
　第２実施形態におけるｐＨ指示薬は、例えば、その変色域（ｐＨ）が３．０～９．０の範囲内にあるものが好ましく、４．０～８．５の範囲内にあるものがより好ましく、４．５～８．０の範囲内にあるものが特に好ましい。 For example, the pH indicator in the second embodiment preferably has a color change range (pH) in the range of 3.0 to 9.0, more preferably in the range of 4.0 to 8.5. Particularly preferred are those in the range of 4.5 to 8.0.
　第２実施形態における保冷用組成物が含有するｐＨ指示薬は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。ただし、通常はｐＨ指示薬を１種のみ含有することが好ましい。 The pH indicator contained in the composition for cold preservation in the second embodiment may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. However, it is usually preferable to contain only one kind of pH indicator.
　第２実施形態における保冷用組成物のｐＨ指示薬の含有量は、保冷用組成物の目的とする色変化が達成される限り特に限定されないが、１～３０ｐｐｍであることが好ましく、５～２０ｐｐｍであることがより好ましい。 The content of the pH indicator in the cold insulation composition in the second embodiment is not particularly limited as long as the intended color change of the cold insulation composition is achieved, but is preferably 1 to 30 ppm, and preferably 5 to 20 ppm. More preferably.
＜その他の成分＞
　第２実施形態における保冷用組成物は、水、無機塩、増粘剤及びｐＨ指示薬以外に、本発明の効果を損なわない範囲内において、これらに該当しないその他の成分を含有していてもよい。前記その他の成分としては、第１実施形態の場合と同様の水以外の溶媒；防腐剤、界面活性剤等の公知の各種添加剤等が挙げられる。
　第２実施形態における保冷用組成物が含有する前記その他の成分は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 <Other ingredients>
The composition for cold preservation in 2nd Embodiment may contain the other component which does not correspond to these in the range which does not impair the effect of this invention other than water, an inorganic salt, a thickener, and a pH indicator. . Examples of the other components include the same solvents other than water as in the first embodiment; various known additives such as preservatives and surfactants.
The said other component which the composition for cold preservation in 2nd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.
　第２実施形態における保冷用組成物の前記その他の成分の含有量は、第１実施形態における保冷用組成物のその他の成分の含有量と同じである。 The content of the other components in the cold insulation composition in the second embodiment is the same as the content of the other components in the cold insulation composition in the first embodiment.
　例えば、第２実施形態での保冷用組成物において、水及び前記溶媒の総含有量に対する前記溶媒の含有量の割合は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることが特に好ましい。
　また、第２実施形態における保冷用組成物の防腐剤の含有量は、特に限定されないが、０．０２～０．５質量％であることが好ましく、０．０４～０．２質量％であることがより好ましい。
　第２実施形態における保冷用組成物は、水及び前記溶媒以外の成分（前記無機塩、増粘剤、ｐＨ指示薬、及び前記溶媒以外のその他の成分）の総含有量に対する、前記無機塩、増粘剤及びｐＨ指示薬の総含有量の割合が、９０質量％以上であることが好ましく、９３質量％以上であることがより好ましく、９６質量％以上であることがさらに好ましく、９８質量％以上であることが特に好ましく、１００質量%であってもよい。前記総含有量の割合が前記下限値以上であることで、保冷用組成物は凍結の前後においてより大きく色変化する。 For example, in the composition for cold preservation in the second embodiment, the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, and preferably 5% by mass or less. More preferred is 2% by mass or less.
Further, the content of the preservative in the composition for cold preservation in the second embodiment is not particularly limited, but is preferably 0.02 to 0.5% by mass, and 0.04 to 0.2% by mass. It is more preferable.
The composition for cold preservation in 2nd Embodiment is the said inorganic salt and increase with respect to the total content of components other than water and the said solvent (The said inorganic salt, a thickener, a pH indicator, and other components other than the said solvent). The ratio of the total content of the adhesive and the pH indicator is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 96% by mass or more, and 98% by mass or more. It is particularly preferable that it may be 100% by mass. When the ratio of the total content is equal to or higher than the lower limit value, the color of the cold-retaining composition changes more greatly before and after freezing.
　第２実施形態における保冷用組成物のｐＨは、４．７～８．０であることが好ましく、５．０～７．７であることがより好ましく、５．２～７．５であることが特に好ましい。
　第２実施形態における保冷用組成物は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度で前記数値範囲のｐＨを示すことが好ましく、前記保冷用組成物の温度が２５℃であるときに前記数値範囲のｐＨをを示すことがより好ましい。
　なお、本実施形態において、保冷用組成物についての単なる「ｐＨ」との記載は、特に断りのない限り、保冷用組成物自体のｐＨを意味するものとする。 The pH of the cold-retaining composition in the second embodiment is preferably 4.7 to 8.0, more preferably 5.0 to 7.7, and 5.2 to 7.5. Is particularly preferred.
It is preferable that the composition for cold preservation in 2nd Embodiment shows pH of the said numerical range at the temperature which the pH indicator melt | dissolves in the said composition for cold preservation, and the temperature of the said composition for cold preservation is 25 degreeC. Sometimes it is more preferred to exhibit a pH in the numerical range.
In addition, in this embodiment, description with mere "pH" about the composition for cold preservation shall mean the pH of the composition for cold preservation itself unless there is particular notice.
　第２実施形態における保冷用組成物は、前記無機塩及び水以外の含有成分をすべて水で置換した場合のｐＨ（α２）が、４．７～８．０であることが好ましく、５．２～７．５であることがより好ましい。
　ｐＨ（α２）は、前記保冷用組成物での含有量（質量％）と同じ含有量（質量％）で前記無機塩のみを含有する無機塩含有水（例えば、無機塩水溶液）のｐＨに相当する。ｐＨ（α２）は、前記保冷用組成物で用いる無機塩の酸性度の指標となるものである。
　ｐＨ（α２）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記無機塩含有水が２５℃であるときのｐＨであることがより好ましい。 The composition for cold preservation in the second embodiment preferably has a pH (α2) of 4.7 to 8.0 when all the components other than the inorganic salt and water are replaced with water. More preferably, it is ˜7.5.
The pH (α2) corresponds to the pH of an inorganic salt-containing water (for example, an inorganic salt aqueous solution) containing only the inorganic salt at the same content (mass%) as the content (mass%) in the composition for cold preservation. To do. The pH (α2) serves as an index of the acidity of the inorganic salt used in the cold insulation composition.
The pH (α2) is preferably the pH at the temperature at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the inorganic salt-containing water is 25 ° C.
　第２実施形態における保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が、６．０～９．１であることが好ましく、６．５～８．６であることがより好ましい。
　ｐＨ（α３）は、前記保冷用組成物での含有量（質量％）と同じ含有量（質量％）で前記増粘剤のみを含有する増粘剤含有水（例えば、増粘剤水溶液）のｐＨに相当する。ｐＨ（α３）は、前記保冷用組成物で用いる増粘剤の酸性度の指標となるものである。
　ｐＨ（α３）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記増粘剤含有水が２５℃であるときのｐＨであることがより好ましい。 The composition for cold preservation in the second embodiment preferably has a pH (α3) of 6.0 to 9.1 when all the components other than the thickener and water are replaced with water. More preferably, it is 5 to 8.6.
pH (α3) is the same as the content (mass%) in the cold insulation composition (mass%) of the thickener-containing water (eg, thickener aqueous solution) containing only the thickener. Corresponds to pH. The pH (α3) serves as an index of the acidity of the thickener used in the cold insulation composition.
The pH (α3) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the thickener-containing water is 25 ° C. .
　第２実施形態における保冷用組成物は、配合成分が異なる点以外は、上述の第１実施形態における保冷用組成物と同じ方法で得られる。 The composition for cold preservation in the second embodiment is obtained by the same method as the composition for cold insulation in the first embodiment described above, except that the blending components are different.
　本発明の第２実施形態に係る保冷具は、前記保冷用組成物を備えたものであり、保冷用組成物が異なる点以外は、上述の第１実施形態に係る保冷具と同様の構成とすることができる。
　本発明の第２実施形態に係る保冷具は、前記保冷用組成物を用いる点以外は、上述の第１実施形態に係る保冷具と同様の方法で得られる。 The cold insulation tool according to the second embodiment of the present invention includes the cold insulation composition, and has the same configuration as the cold insulation tool according to the first embodiment except that the cold insulation composition is different. can do.
The cold insulator according to the second embodiment of the present invention is obtained by the same method as the cold insulator according to the first embodiment described above, except that the cold insulation composition is used.
　第２実施形態における保冷用組成物は、凍結の前後において大きく色変化するために、凍結の有無を容易に視認可能である。そして、保冷用組成物のこの色変化が、保冷具の外側から視認可能となっている。これにより保冷具は、所望の温度にまで十分に冷却されているか否かが容易に視認可能となっている。
　また、前記保冷用組成物は、凍結及び解凍を繰り返すなど、冷却及び昇温を繰り返しても、効果が損なわれることがない。従って、前記保冷用組成物を備えた保冷具は、繰り返し利用にも適している。 Since the composition for cold preservation in the second embodiment largely changes in color before and after freezing, the presence or absence of freezing can be easily visually confirmed. And this color change of the composition for cold insulation is visible from the outer side of a cold insulator. Thereby, it is possible to easily visually check whether the cold insulator is sufficiently cooled to a desired temperature.
The effect of the cold-retaining composition is not impaired even when the cooling and heating are repeated, such as repeated freezing and thawing. Therefore, the cold insulator provided with the cold-retaining composition is also suitable for repeated use.
＜＜第３実施形態＞＞
　本発明の第３実施形態に係る保冷具は、水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩を含有し、前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩の含有量の割合が、５～１００質量％であり、前記保冷用組成物は、前記無機塩及び水以外の含有成分をすべて水で置換した場合のｐＨ（α２）が７以下となるものであり、前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が７以上となるものであり、ｐＨ（α２）及びｐＨ（α３）が、前記ｐＨ指示薬の変色域よりも低いｐＨ、変色域のｐＨ、及び変色域よりも高いｐＨの３つのｐＨ域のうち、互いに異なるｐＨ域の値を示す。 << Third Embodiment >>
The cold insulation tool according to the third embodiment of the present invention is a cold insulation tool provided with a cold insulation composition containing water, an inorganic salt, a thickener, and a pH indicator, wherein the cold insulation composition is the inorganic salt. The aqueous solution contains an acidic inorganic salt exhibiting acidity, and in the composition for cold preservation, the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass. Yes, the cold-retaining composition has a pH (α2) of 7 or less when all the components other than the inorganic salt and water are replaced with water, and the cold-retaining composition is the thickener PH (α3) when all components other than water and water are replaced with water is 7 or more, and pH (α2) and pH (α3) are lower than the color change range of the pH indicator, discoloration Of the three pH ranges, the pH of the range and the pH higher than the color change range, Shows the different values of pH range are.
　前記保冷具の保冷用組成物の色は、保冷用組成物の凍結の前後において大きく変化する。ここで、保冷用組成物の色は、、ｐＨ指示薬の発色の有無が反映されたものである。そのため、前記保冷具は、冷却状態が目的とする状態（対象物を十分に冷却できる状態）にあるか容易に視認可能となっている。そして、凍結の前後における保冷用組成物の色は、前記無機塩、増粘剤等のｐＨ指示薬以外の含有成分自体の色を主として反映したものではない。 The color of the cold insulation composition of the cold insulation tool varies greatly before and after freezing of the cold insulation composition. Here, the color of the composition for cold preservation reflects the presence or absence of color development of the pH indicator. Therefore, the cold insulator can be easily visually confirmed whether the cooling state is in a target state (a state in which the object can be sufficiently cooled). And the color of the composition for cold preservation before and after freezing does not mainly reflect the color of components other than pH indicators, such as the said inorganic salt and a thickener.
　第３実施形態における保冷用組成物は、その酸性度に影響を与える成分として、無機塩及び増粘剤を含有する。そして、前記保冷用組成物においては、前記無機塩として酸性の無機塩を選択し、その含有量を限定し、無機塩及び増粘剤の酸性度を限定して、さらにこれら無機塩及び増粘剤に対して、適した変色域を有するｐＨ指示薬を組み合わせて用いている。このような構成を有する前記保冷用組成物は、ｐＨ指示薬の発色の変化又は有無に依存して、顕著に大きく色変化する。 The composition for cold preservation in the third embodiment contains an inorganic salt and a thickener as components that affect the acidity. And in the composition for cold preservation, an acidic inorganic salt is selected as the inorganic salt, the content is limited, the acidity of the inorganic salt and the thickener is limited, and these inorganic salts and thickeners are further limited. A pH indicator having a suitable color change range is used in combination with the agent. The cold-retaining composition having such a configuration changes color remarkably greatly depending on the change in color presence or absence of the pH indicator.
＜無機塩＞
　第３実施形態における前記無機塩は、保冷剤の一成分として機能し、主にその種類及び量により、保冷用組成物の凍結温度が決定される。
　また、前記無機塩は、前記ｐＨ指示薬に該当しない成分であり、保冷用組成物の凍結時に、結晶又はアモルファス（非晶質）として析出し、その析出の有無によって、保冷用組成物の色変化に関与する。 <Inorganic salt>
The said inorganic salt in 3rd Embodiment functions as one component of a cryogen, and the freezing temperature of the composition for cold preservation is mainly determined by the kind and quantity.
The inorganic salt is a component that does not correspond to the pH indicator, and precipitates as crystals or amorphous (amorphous) at the time of freezing of the cold insulation composition, and the color change of the cold insulation composition depends on the presence or absence of the precipitation. Involved in.
　第３実施形態における前記保冷用組成物は、前記無機塩として、その水溶液が酸性を示す酸性の無機塩を含有する。 The said composition for cold preservation in 3rd Embodiment contains the acidic inorganic salt in which the aqueous solution shows acidity as said inorganic salt.
［酸性の無機塩］
　第３実施形態における前記酸性の無機塩は、特に限定されず、目的に応じて適宜選択でき、非水和物であってもよいし、水和物であってもよい。
　第３実施形態における酸性の無機塩で好ましいものとしては、例えば、第１実施形態におけるリン酸二水素塩以外の無機塩と同じもの、すなわち、塩化アンモニウム（ＮＨ４Ｃｌ）、塩化マグネシウム（ＭｇＣｌ２）、硫酸アンモニウム（（ＮＨ４）２ＳＯ４）、硝酸アンモニウム（ＮＨ４ＮＯ３）、硫酸アルミニウム（Ａｌ２（ＳＯ４）３）、ミョウバン（ＡｌＫ（ＳＯ４）２）、アンモニウムミョウバン（Ａｌ（ＮＨ４）（ＳＯ４）２）、硝酸カルシウム四水和物（Ｃａ（ＮＯ３）２・４Ｈ２Ｏ）、硝酸カルシウム（Ｃａ（ＮＯ３）２）等が挙げられ、塩化アンモニウムが好ましい。 [Acid inorganic salt]
The acidic inorganic salt in the third embodiment is not particularly limited and can be appropriately selected depending on the purpose, and may be a non-hydrate or a hydrate.
Preferable acidic inorganic salts in the third embodiment are, for example, the same inorganic salts other than dihydrogen phosphate in the first embodiment, that is, ammonium chloride (NH 4 Cl), magnesium chloride (MgCl 2 ). ), Ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium nitrate (NH 4 NO 3 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), alum (AlK (SO 4 ) 2 ), ammonium alum (Al (NH 4) ) (SO 4 ) 2 ), calcium nitrate tetrahydrate (Ca (NO 3 ) 2 .4H 2 O), calcium nitrate (Ca (NO 3 ) 2 ) and the like, and ammonium chloride is preferred.
　第３実施形態における保冷用組成物が含有する前記酸性の無機塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The acidic inorganic salt contained in the composition for cold preservation in the third embodiment may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. .
［その他の無機塩］
　第３実施形態における保冷用組成物は、前記無機塩として、前記酸性の無機塩以外に、その他の無機塩を含有していてもよい。
　前記その他の無機塩は、非水和物であってもよいし、水和物であってもよい。 [Other inorganic salts]
The composition for cold preservation in 3rd Embodiment may contain other inorganic salt other than the said acidic inorganic salt as said inorganic salt.
The other inorganic salts may be non-hydrates or hydrates.
　第３実施形態における前記その他の無機塩は、本発明の効果を損なわない限り特に限定されないが、例えば、その水溶液が中性を示す中性の無機塩、その水溶液が塩基性を示す塩基性の無機塩等が挙げられる。 The other inorganic salt in the third embodiment is not particularly limited as long as the effects of the present invention are not impaired. For example, the neutral inorganic salt whose aqueous solution shows neutrality, and the basic salt whose aqueous solution shows basicity. An inorganic salt etc. are mentioned.
　前記中性の無機塩としては、例えば、第１実施形態における前記中性の無機塩と同じものが挙げられ、塩化ナトリウム又は塩化カリウムであることが好ましい。 Examples of the neutral inorganic salt include the same neutral inorganic salt as in the first embodiment, and sodium chloride or potassium chloride is preferable.
　前記塩基性の無機塩は、リン酸塩及びリン酸一水素塩以外の無機塩であることが好ましく、例えば、第１実施形態における前記リン酸塩以外の塩基性の無機塩と同じものが挙げられ、炭酸ナトリウム又は炭酸カリウムであることが好ましい。 The basic inorganic salt is preferably an inorganic salt other than phosphate and monohydrogen phosphate, and examples thereof include the same basic inorganic salts other than the phosphate in the first embodiment. And is preferably sodium carbonate or potassium carbonate.
　第３実施形態における保冷用組成物が含有する前記その他の無機塩は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The said other inorganic salt which the composition for cold preservation in 3rd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .
　第３実施形態での保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩の含有量の割合は、５～１００質量％であり、例えば、２０～８０質量％、４０～６０質量％等とすることができるが、これらに限定されない。
　このような数値範囲の中で、前記割合の下限値としては、上記の２０質量％、４０質量％以外にも、例えば、１０質量％、３０質量％、４５質量％等が選択できるが、これらに限定されない。また、このような数値範囲の中で、前記割合の上限値としては、上記の８０質量％、６０質量％以外にも、例えば、９０質量％、７０質量％、５５質量％等が選択できるが、これらに限定されない。 In the composition for cold preservation in the third embodiment, the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass, for example, 20 to 80% by mass, 40% It can be set to ˜60% by mass, but is not limited thereto.
In such a numerical range, as the lower limit of the ratio, in addition to 20% by mass and 40% by mass, for example, 10% by mass, 30% by mass, 45% by mass, etc. can be selected. It is not limited to. Further, in such a numerical range, as the upper limit value of the ratio, for example, 90% by mass, 70% by mass, 55% by mass and the like can be selected in addition to the above 80% by mass and 60% by mass. However, it is not limited to these.
　第３実施形態における凍結前、好ましくは０℃以上の保冷用組成物中で、前記無機塩の溶解量は多いほど好ましく、前記無機塩の総量のうち溶解している量が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがさらに好ましく、１００質量％（全量）であってもよい。
　また、第３実施形態における凍結後の保冷用組成物中で、前記無機塩の析出量は多いほど好ましく、前記無機塩の総量のうち析出している量が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることがさらに好ましく、１００質量％（全量）であってもよい。 Before freezing in the third embodiment, preferably in the cold-retaining composition at 0 ° C. or higher, the amount of the inorganic salt dissolved is preferably as large as possible, and the amount dissolved in the total amount of the inorganic salt is 90% by mass or more. Preferably, it is 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
Moreover, in the composition for cold preservation after freezing in 3rd Embodiment, it is so preferable that there is much precipitation amount of the said inorganic salt, and it is preferable that the amount which has precipitated among the total amount of the said inorganic salt is 90 mass% or more. 95% by mass or more, more preferably 98% by mass or more, and may be 100% by mass (total amount).
　第３実施形態における保冷用組成物の無機塩の総含有量は、５～３５質量％であることが好ましく、１０～３０質量％であることがより好ましく、１５～２５質量％であることが特に好ましい。 In the third embodiment, the total content of the inorganic salt of the composition for cold insulation is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and 15 to 25% by mass. Particularly preferred.
＜増粘剤＞
　第３実施形態における前記増粘剤は、保冷用組成物の粘度を増大させ、前記ｐＨ指示薬に該当しない成分である。第３実施形態における前記増粘剤は、保冷用組成物の凍結時に析出しないものが好ましい。なお、本明細書において「増粘剤が保冷用組成物の凍結時に析出しない」とは、第１実施形態において、先に説明したとおりである。 <Thickener>
The thickener in the third embodiment is a component that increases the viscosity of the cold-retaining composition and does not correspond to the pH indicator. The thickener in the third embodiment is preferably one that does not precipitate when the composition for cold preservation is frozen. In the present specification, “the thickener does not precipitate when the composition for cold preservation is frozen” is as described above in the first embodiment.
　第３実施形態における前記増粘剤としては、例えば、第１実施形態における増粘剤と同じものが挙げられる。
　第１実施形態の場合と同様に、第３実施形態における前記増粘剤は、アクリル系ポリマー、カルボキシアルキルセルロース、キサンタンガム、グアーガム、ヒドロキシアルキルグアーガム、ペクチン、タマリンドガム、カラギーナン及びアルキレングリコールからなる群から選択される１種以上であることが好ましい。
　そして、前記増粘剤は、アクリル系ポリマー、カルボキシアルキルセルロース、キサンタンガム、グアーガム及びヒドロキシアルキルグアーガムからなる群から選択される１種以上であることがより好ましい。
　このような増粘剤を用いることで、保冷用組成物は、凍結の前後における色変化が大きく、かつ取り扱い性により優れたものとなる。 As said thickener in 3rd Embodiment, the same thing as the thickener in 1st Embodiment is mentioned, for example.
As in the case of the first embodiment, the thickener in the third embodiment is selected from the group consisting of acrylic polymer, carboxyalkyl cellulose, xanthan gum, guar gum, hydroxyalkyl guar gum, pectin, tamarind gum, carrageenan and alkylene glycol. It is preferable that it is 1 or more types selected.
The thickener is more preferably one or more selected from the group consisting of acrylic polymers, carboxyalkyl cellulose, xanthan gum, guar gum and hydroxyalkyl guar gum.
By using such a thickener, the composition for cold preservation has a large color change before and after freezing and is excellent in handleability.
　第３実施形態における保冷用組成物が含有する増粘剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 The thickener contained in the composition for cold insulation in the third embodiment may be only one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
　第３実施形態における凍結前及び凍結後の保冷用組成物中で、増粘剤の析出量は少ないほど好ましく、増粘剤の総量のうち析出している量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることがさらに好ましく、０質量％である（全量が析出していない）ことが特に好ましい。 In the composition for cold preservation before freezing and after freezing in the third embodiment, the amount of the thickener deposited is preferably as small as possible, and the amount deposited in the total amount of the thickener is 10% by mass or less. It is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 0% by mass (the total amount is not precipitated).
　第３実施形態における保冷用組成物の増粘剤の含有量は、０．１～１０質量％であることが好ましく、０．３～６質量％であることがより好ましく、０．６～３質量％であることが特に好ましい。 In the third embodiment, the content of the thickener in the composition for cold preservation is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and 0.6 to 3%. It is particularly preferable that the content is% by mass.
＜ｐＨ指示薬＞
　第３実施形態における前記ｐＨ指示薬（酸塩基指示薬）は、その発色の有無を反映させて保冷用組成物の色を決定する成分である。保冷用組成物は、ｐＨ指示薬を含有することにより、凍結の前後において色変化する。 <PH indicator>
The pH indicator (acid-base indicator) in the third embodiment is a component that determines the color of the composition for cold preservation by reflecting the presence or absence of color development. The composition for cold preservation changes a color before and after freezing by containing a pH indicator.
　第３実施形態における前記ｐＨ指示薬は、特に限定されないが、ｐＫａが４．０～７．５であるものが好ましい。
　なお、本実施形態におけるｐＨ指示薬のｐＫａは、特に断りのない限り、溶媒が水で温度が２５℃である場合の値を意味する。
　第３実施形態における前記ｐＨ指示薬としては、例えば、第１実施形態におけるｐＨ指示薬と同じものが挙げられる。 The pH indicator in the third embodiment is not particularly limited, but preferably has a pKa of 4.0 to 7.5.
In addition, unless otherwise indicated, pKa of the pH indicator in this embodiment means the value in case a solvent is water and temperature is 25 degreeC.
As said pH indicator in 3rd Embodiment, the same thing as the pH indicator in 1st Embodiment is mentioned, for example.
　第３実施形態におけるｐＨ指示薬は、例えば、その変色域（ｐＨ）が３．０～１０．５の範囲内にあるものが好ましく、３．３～９．５の範囲内にあるものがより好ましく、３．５～９．０の範囲内にあるものが特に好ましい。 The pH indicator in the third embodiment, for example, preferably has a color change range (pH) in the range of 3.0 to 10.5, more preferably in the range of 3.3 to 9.5. And those in the range of 3.5 to 9.0 are particularly preferred.
　第３実施形態における保冷用組成物が含有するｐＨ指示薬は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。ただし、通常はｐＨ指示薬を１種のみ含有することが好ましい。 The pH indicator contained in the composition for cold preservation in the third embodiment may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. However, it is usually preferable to contain only one kind of pH indicator.
　第３実施形態における保冷用組成物のｐＨ指示薬の含有量は、保冷用組成物の目的とする色変化が達成される限り特に限定されないが、１～３０ｐｐｍであることが好ましく、５～２０ｐｐｍであることがより好ましい。 The content of the pH indicator in the cold insulation composition in the third embodiment is not particularly limited as long as the intended color change of the cold insulation composition is achieved, but is preferably 1 to 30 ppm, and is preferably 5 to 20 ppm. More preferably.
＜その他の成分＞
　第３実施形態における保冷用組成物は、水、無機塩、増粘剤及びｐＨ指示薬以外に、本発明の効果を損なわない範囲内において、これらに該当しないその他の成分を含有していてもよい。前記その他の成分としては、第１実施形態の場合と同様の水以外の溶媒；防腐剤、界面活性剤等の公知の各種添加剤等が挙げられる。
　第３実施形態における保冷用組成物が含有する前記その他の成分は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は、任意に選択できる。 <Other ingredients>
The composition for cold preservation in 3rd Embodiment may contain the other component which does not correspond to these in the range which does not impair the effect of this invention other than water, an inorganic salt, a thickener, and a pH indicator. . Examples of the other components include the same solvents other than water as in the first embodiment; various known additives such as preservatives and surfactants.
The said other component which the composition for cold preservation in 3rd Embodiment contains may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.
　第３実施形態における保冷用組成物の前記その他の成分の含有量は、第１実施形態における保冷用組成物のその他の成分の含有量と同じである。 The content of the other components in the cold insulation composition in the third embodiment is the same as the content of the other components in the cold insulation composition in the first embodiment.
　例えば、第３実施形態での保冷用組成物において、水及び前記溶媒の総含有量に対する前記溶媒の含有量の割合は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることが特に好ましい。
　また、第３実施形態における保冷用組成物の防腐剤の含有量は、特に限定されないが、０．０２～０．５質量％であることが好ましく、０．０４～０．２質量％であることがより好ましい。
　第３実施形態における保冷用組成物は、水及び前記溶媒以外の成分（前記無機塩、増粘剤、ｐＨ指示薬、及び前記溶媒以外のその他の成分）の総含有量に対する、前記無機塩、増粘剤及びｐＨ指示薬の総含有量の割合が、９０質量％以上であることが好ましく、９３質量％以上であることがより好ましく、９６質量％以上であることがさらに好ましく、９８質量％以上であることが特に好ましく、１００質量%であってもよい。前記総含有量の割合が前記下限値以上であることで、保冷用組成物は凍結の前後においてより大きく色変化する。 For example, in the composition for cold preservation in the third embodiment, the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, and preferably 5% by mass or less. More preferred is 2% by mass or less.
Further, the content of the preservative in the composition for cold preservation in the third embodiment is not particularly limited, but is preferably 0.02 to 0.5% by mass, and 0.04 to 0.2% by mass. It is more preferable.
The composition for cold preservation in the third embodiment includes the inorganic salt, the increase in the total content of components other than water and the solvent (the inorganic salt, the thickener, the pH indicator, and other components other than the solvent). The ratio of the total content of the adhesive and the pH indicator is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 96% by mass or more, and 98% by mass or more. It is particularly preferable that it may be 100% by mass. When the ratio of the total content is equal to or higher than the lower limit value, the color of the cold-retaining composition changes more greatly before and after freezing.
　第３実施形態における保冷用組成物は、前記無機塩及び水以外の含有成分をすべて水で置換した場合のｐＨ（α２）が７以下となるものである。
　ｐＨ（α２）は、前記保冷用組成物での含有量（質量％）と同じ含有量（質量％）で前記無機塩のみを含有する無機塩含有水（例えば、無機塩水溶液）のｐＨに相当する。ｐＨ（α２）は、前記保冷用組成物で用いる無機塩の酸性度の指標となるものである。
　ｐＨ（α２）は３．５～７．０であることが好ましく、４．０～６．６であることがより好ましく、４．５～６．３であることが特に好ましい。 The composition for cold preservation in the third embodiment has a pH (α2) of 7 or less when all the components other than the inorganic salt and water are replaced with water.
The pH (α2) corresponds to the pH of an inorganic salt-containing water (for example, an inorganic salt aqueous solution) containing only the inorganic salt at the same content (mass%) as the content (mass%) in the composition for cold preservation. To do. The pH (α2) serves as an index of the acidity of the inorganic salt used in the cold insulation composition.
The pH (α2) is preferably 3.5 to 7.0, more preferably 4.0 to 6.6, and particularly preferably 4.5 to 6.3.
　ｐＨ（α２）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記無機塩含有水が２５℃であるときのｐＨであることがより好ましい。 The pH (α2) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the inorganic salt-containing water is 25 ° C.
　第３実施形態における保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が７以上となるものである。
　ｐＨ（α３）は、前記保冷用組成物での含有量（質量％）と同じ含有量（質量％）で前記増粘剤のみを含有する増粘剤含有水（例えば、増粘剤水溶液）のｐＨに相当する。ｐＨ（α３）は、前記保冷用組成物で用いる増粘剤の酸性度の指標となるものである。
　ｐＨ（α３）は７．０～９．５であることが好ましく、７．０～９．０であることがより好ましく、７．０～８．５であることが特に好ましい。 The composition for cold preservation in the third embodiment has a pH (α3) of 7 or more when all the components other than the thickener and water are replaced with water.
pH (α3) is the same as the content (mass%) in the cold insulation composition (mass%) of the thickener-containing water (eg, thickener aqueous solution) containing only the thickener. Corresponds to pH. The pH (α3) serves as an index of the acidity of the thickener used in the cold insulation composition.
The pH (α3) is preferably from 7.0 to 9.5, more preferably from 7.0 to 9.0, and particularly preferably from 7.0 to 8.5.
　ｐＨ（α３）は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度でのｐＨであることが好ましく、前記増粘剤含有水が２５℃であるときのｐＨであることがより好ましい。 The pH (α3) is preferably the pH at which the pH indicator is dissolved in the cold-retaining composition, and more preferably the pH when the thickener-containing water is 25 ° C. .
　第３実施形態における保冷用組成物は、ｐＨ（α２）及びｐＨ（α３）が、前記ｐＨ指示薬の変色域よりも低いｐＨ、変色域のｐＨ、及び変色域よりも高いｐＨの３つのｐＨ域のうち、互いに異なるｐＨ域の値を示すものである。 The composition for cold preservation in the third embodiment has three pH ranges in which pH (α2) and pH (α3) are lower than the color change range of the pH indicator, the pH of the color change range, and the pH higher than the color change range. Among them, values in different pH ranges are shown.
　第３実施形態における保冷用組成物のｐＨは、４．１～７．４であることが好ましく、４．４～７．１であることがより好ましく、４．６～６．９であることが特に好ましい。
　第３実施形態における保冷用組成物は、ｐＨ指示薬が前記保冷用組成物中で溶解している温度で前記数値範囲のｐＨを示すことが好ましく、前記保冷用組成物の温度が２５℃であるときに前記数値範囲のｐＨをを示すことがより好ましい。
　なお、本実施形態において、保冷用組成物についての単なる「ｐＨ」との記載は、特に断りのない限り、保冷用組成物自体のｐＨを意味するものとする。 The pH of the cold-retaining composition in the third embodiment is preferably 4.1 to 7.4, more preferably 4.4 to 7.1, and 4.6 to 6.9. Is particularly preferred.
The cold-retaining composition in the third embodiment preferably exhibits a pH in the numerical range at a temperature at which the pH indicator is dissolved in the cold-retaining composition, and the temperature of the cold-retaining composition is 25 ° C. Sometimes it is more preferred to exhibit a pH in the numerical range.
In addition, in this embodiment, description with mere "pH" about the composition for cold preservation shall mean the pH of the composition for cold preservation itself unless there is particular notice.
　第３実施形態における保冷用組成物は、配合成分が異なる点以外は、上述の第１実施形態における保冷用組成物と同じ方法で得られる。 The composition for cold insulation in the third embodiment is obtained by the same method as the composition for cold insulation in the first embodiment described above, except that the blending components are different.
　本発明の第３実施形態に係る保冷具は、前記保冷用組成物を備えたものであり、保冷用組成物が異なる点以外は、上述の第１実施形態に係る保冷具と同様の構成とすることができる。
　本発明の第３実施形態に係る保冷具は、前記保冷用組成物を用いる点以外は、上述の第１実施形態に係る保冷具と同様の方法で得られる。 The cold insulation tool according to the third embodiment of the present invention is provided with the cold insulation composition, and has the same configuration as the cold insulation tool according to the first embodiment except that the cold insulation composition is different. can do.
The cold insulator according to the third embodiment of the present invention is obtained by the same method as the cold insulator according to the first embodiment described above, except that the cold insulating composition is used.
　第３実施形態における保冷用組成物は、凍結の前後において大きく色変化するために、凍結の有無を容易に視認可能である。そして、保冷用組成物のこの色変化が、保冷具の外側から視認可能となっている。これにより保冷具は、所望の温度にまで十分に冷却されているか否かが容易に視認可能となっている。
　また、前記保冷用組成物は、凍結及び解凍を繰り返すなど、冷却及び昇温を繰り返しても、効果が損なわれることがない。従って、前記保冷用組成物を備えた保冷具は、繰り返し利用にも適している。 Since the composition for cold preservation in the third embodiment largely changes in color before and after freezing, the presence or absence of freezing can be easily visually confirmed. And this color change of the composition for cold insulation is visible from the outer side of a cold insulator. Thereby, it is possible to easily visually check whether the cold insulator is sufficiently cooled to a desired temperature.
The effect of the cold-retaining composition is not impaired even when the cooling and heating are repeated, such as repeated freezing and thawing. Therefore, the cold insulator provided with the cold-retaining composition is also suitable for repeated use.
　以下、具体的実施例により、本発明についてより詳細に説明する。ただし、本発明は、以下に示す実施例に、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
　本実施例及び比較例で使用した原料を、以下に示す。
（増粘剤）
　・ＨＰＧ１（ヒドロキシプロピルグアーガム）：三晶社製「メイプロＨＰＧ８１１１」
　・ＣＭＣ（カルボキシメチルセルロース）：第一工業製薬社製「セロゲン」
　・ＣＶＰ（カルボキシビニルポリマー）：東亜合成社製「レオジック２７０」
（ｐＨ指示薬）
　・ＢＣＰ：ブロモクレゾールパープル（和光純薬社製）
　・ＰＲ：フェノールレッド（和光純薬社製）
　・ＢＴＢ：ブロモチモールブルー（和光純薬社製）
　・ＭＲ：メチルレッド（和光純薬社製）
　・ＢＣＧ：ブロモクレゾールグリーン（和光純薬社製）
（防腐剤）
　三愛石油社製「ソジウムオマジン」 The raw materials used in the examples and comparative examples are shown below.
(Thickener)
HPG1 (hydroxypropyl guar gum): “Meipro HPG8111” manufactured by Sankisha
・ CMC (Carboxymethylcellulose): “Serogen” manufactured by Daiichi Kogyo Seiyaku
CVP (carboxy vinyl polymer): “Reogic 270” manufactured by Toa Gosei Co., Ltd.
(PH indicator)
・ BCP: Bromocresol purple (Wako Pure Chemical Industries, Ltd.)
・ PR: Phenol red (manufactured by Wako Pure Chemical Industries)
・ BTB: Bromothymol Blue (manufactured by Wako Pure Chemical Industries, Ltd.)
・ MR: Methyl Red (manufactured by Wako Pure Chemical Industries)
・ BCG: Bromocresol Green (Wako Pure Chemical Industries, Ltd.)
(Preservative)
"Sodium Omagine" manufactured by Sanai Oil Co., Ltd.
［実施例１］
＜保冷用組成物及び保冷具（第１実施形態）の製造＞
　室温（２０～２５℃）下において、水（７９．１６質量部）にＢＣＰを添加して溶解させ、次いで、さらに塩化アンモニウム（９．７２質量部）、塩化カリウム（９．７２質量部）、リン酸三ナトリウム十二水和物（０．１５質量部）及びリン酸二水素アンモニウム（０．１０質量部）を添加して溶解させ、次いで、ＨＰＧ１（１．１０質量部）を添加して、室温下のままで１時間撹拌して溶解させ、得られた液状物が十分に増粘していることを確認した後、防腐剤（０．０５質量部）を添加して、室温下のままで３０分間撹拌することにより保冷用組成物を得た。このとき、ＢＣＰの配合量は、得られた保冷用組成物での含有量が８ｐｐｍとなるように調節した。各配合成分及びその保冷用組成物での含有量を表２に示す。なお、表２中、配合成分の欄の「塩基性の塩」とは、リン酸塩及びリン酸一水素塩以外の塩基性の塩を意味する。また、リン酸三ナトリウム十二水和物は、結晶水（１２Ｈ２Ｏ）を省略して記載している。これらは、以降の表においても同様である。 [Example 1]
<Manufacture of composition for cold preservation and cold insulation tool (first embodiment)>
Under room temperature (20-25 ° C.), BCP was added and dissolved in water (79.16 parts by mass), and then ammonium chloride (9.72 parts by mass), potassium chloride (9.72 parts by mass), Trisodium phosphate dodecahydrate (0.15 parts by mass) and ammonium dihydrogen phosphate (0.10 parts by mass) were added and dissolved, and then HPG1 (1.10 parts by mass) was added. The mixture was stirred for 1 hour at room temperature and dissolved, and after confirming that the obtained liquid was sufficiently thickened, an antiseptic (0.05 parts by mass) was added, The composition for cold preservation was obtained by stirring for 30 minutes. At this time, the compounding quantity of BCP was adjusted so that content in the obtained composition for cold preservation might be 8 ppm. Table 2 shows the content of each compounding component and its composition for cold storage. In Table 2, “basic salt” in the column of the blending component means a basic salt other than phosphate and monohydrogen phosphate. In addition, trisodium phosphate dodecahydrate is described by omitting crystal water (12H 2 O). The same applies to the following tables.
　また、ｐＨ（α１）、ｐＨ（α２）、ｐＨ（α３）、溶媒が水で温度が２５℃である場合のｐＨ指示薬のｐＫａ、保冷用組成物のｐＨ等の物性を表７に示す。ｐＨ（α１）、ｐＨ（α２）、ｐＨ（α３）及び前記ｐＨは、いずれも測定対象物の温度を２５℃として測定した。得られた保冷用組成物における、無機塩の総含有量に対する、酸性の無機塩及びリン酸塩の合計含有量の割合（以下、この値を符号「（Ｘ１）」で示すことがある）も表７に示している。 Table 7 shows physical properties such as pH (α1), pH (α2), pH (α3), pH indicator pKa when the solvent is water and the temperature is 25 ° C., and the pH of the composition for cold preservation. The pH (α1), pH (α2), pH (α3) and the pH were all measured with the temperature of the measurement object being 25 ° C. The ratio of the total content of the acidic inorganic salt and the phosphate to the total content of the inorganic salt in the obtained composition for cold insulation (hereinafter, this value may be indicated by the symbol “(X1)”) Table 7 shows.
　次いで、得られた保冷用組成物を高密度ポリエチレン製の容器に封入して、第１実施形態の保冷具を得た。 Next, the obtained cold insulation composition was sealed in a container made of high density polyethylene to obtain the cold insulation tool of the first embodiment.
＜保冷用組成物の評価＞
（色変化）
　得られた保冷用組成物（保冷具）を－２５℃まで冷却した。この間、保冷用組成物は、－２５℃よりも高い温度で凍結すると共に、凍結の前後で色変化した。そして、この凍結前後での保冷用組成物の色変化を、下記基準にしたがって目視で評価した。結果を表９に示す。表９には、用いたｐＨ指示薬の変色域及び色変化もあわせて示す。 <Evaluation of composition for cold preservation>
(Color change)
The obtained composition for cold insulation (cold insulation tool) was cooled to -25 ° C. During this time, the composition for cold preservation was frozen at a temperature higher than −25 ° C. and changed in color before and after freezing. And the color change of the composition for cold preservation before and behind this freezing was evaluated visually according to the following reference | standard. The results are shown in Table 9. Table 9 also shows the color change range and color change of the pH indicator used.
　なお、表９において、評価結果の欄に記載されている「色変化」とは、凍結前後での保冷用組成物の色変化を示し、例えば、「緑→黄」とは、保冷用組成物の色が凍結前は緑色で凍結後は黄色であったことを示す。
　○：凍結前後での色変化が大きく、冷却状態の視認が極めて容易である。
　△：凍結前後での色変化が判別可能であり、冷却状態の視認が可能である。
　×：凍結前後での色変化が不明瞭であり、冷却状態の視認が困難又は不可能である。 In Table 9, “color change” described in the evaluation result column indicates a color change of the cold-retaining composition before and after freezing. For example, “green → yellow” means a cold-retaining composition. Indicates that the color was green before freezing and yellow after freezing.
○: The color change before and after freezing is large and the cooling state is very easy to visually recognize.
(Triangle | delta): The color change before and behind freezing can be discriminate | determined and the visual recognition of a cooling state is possible.
X: The color change before and after freezing is unclear, and it is difficult or impossible to visually recognize the cooling state.
　また、表９において、ｐＨ指示薬の変色域の欄に記載されている「低ｐＨ→高ｐＨ色変化」とは、ｐＨ指示薬が含有されている液体のｐＨが、特定の値からこれよりも高い値へ変化した際に、ｐＨ指示薬が変色域内で示す色変化を示し、例えば、「黄→紫」とは、前記液体のｐＨが高くなる過程で、ｐＨ指示薬が前記液体を黄色から紫色に色変化させることを示す。 Further, in Table 9, “low pH → high pH color change” described in the column of the color change region of the pH indicator means that the pH of the liquid containing the pH indicator is higher than a specific value. When the pH indicator changes to a value, the pH indicator shows the color change within the color change range.For example, “yellow → purple” means that the pH indicator changes the color of the liquid from yellow to purple in the process of increasing the pH of the liquid. Indicates to change.
＜保冷用組成物及び保冷具（第１実施形態）の製造、保冷用組成物の評価＞
［実施例２～１３］
　保冷用組成物の配合成分及びその保冷用組成物での含有量を表２及び３に示すとおりとした点以外は、実施例１と同じ方法で、第１実施形態の保冷用組成物及び保冷具を製造し、保冷用組成物を評価した。保冷用組成物の各物性を表７に、評価結果を表９に、それぞれ示す。 <Manufacture of composition for cold preservation and cold insulation tool (first embodiment), evaluation of composition for cold insulation>
[Examples 2 to 13]
The composition for cold insulation and the cold insulation of the first embodiment are the same as those of Example 1, except that the components of the cold insulation composition and the content in the cold insulation composition are as shown in Tables 2 and 3. A tool was manufactured and a cold insulation composition was evaluated. Table 7 shows the physical properties of the cold insulation composition, and Table 9 shows the evaluation results.
［実施例１４］
＜保冷用組成物及び保冷具（第２実施形態）の製造＞
　室温（２０～２５℃）下において、水（７８．９０質量部）にＢＣＰを添加して溶解させ、次いで、さらに塩化アンモニウム（９．７０質量部）、塩化カリウム（９．７０質量部）及びリン酸水素二アンモニウム（０．５０質量部）を添加して溶解させ、次いで、ＣＭＣ（１．１０質量部）を添加して、室温下のままで１時間撹拌して溶解させ、得られた液状物が十分に増粘していることを確認した後、防腐剤（０．０５質量部）を添加して、室温下のままで３０分間撹拌することにより保冷用組成物を得た。このとき、ＢＣＰの配合量は、得られた保冷用組成物での含有量が８ｐｐｍとなるように調節した。各配合成分及びその保冷用組成物での含有量を表３に示す。 [Example 14]
<Manufacture of composition for cold preservation and cold insulation tool (second embodiment)>
Under room temperature (20 to 25 ° C.), BCP is added and dissolved in water (78.90 parts by mass), and then ammonium chloride (9.70 parts by mass), potassium chloride (9.70 parts by mass) and Obtained by adding diammonium hydrogen phosphate (0.50 parts by mass) and then dissolving CMC (1.10 parts by mass) while stirring at room temperature for 1 hour After confirming that the liquid was sufficiently thickened, a preservative (0.05 parts by mass) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a composition for cold preservation. At this time, the compounding quantity of BCP was adjusted so that content in the obtained composition for cold preservation might be 8 ppm. Table 3 shows the content of each compounding component and its composition for cold storage.
　また、ｐＨ（α１）、ｐＨ（α２）、ｐＨ（α３）、溶媒が水で温度が２５℃である場合のｐＨ指示薬のｐＫａ、保冷用組成物のｐＨ等の物性を表７に示す。ｐＨ（α１）、ｐＨ（α２）、ｐＨ（α３）及び前記ｐＨは、いずれも測定対象物の温度を２５℃として測定した。得られた保冷用組成物における、無機塩の総含有量に対する、酸性の無機塩及びリン酸一水素塩の合計含有量の割合（以下、この値を符号「（Ｘ２）」で示すことがある）と、水、無機塩及び増粘剤の総含有量に対する、リン酸一水素塩の含有量の割合（以下、この値を符号「（Ｘ３）」で示すことがある）も表７に示している。 Table 7 shows physical properties such as pH (α1), pH (α2), pH (α3), pH indicator pKa when the solvent is water and the temperature is 25 ° C., and the pH of the composition for cold preservation. The pH (α1), pH (α2), pH (α3) and the pH were all measured with the temperature of the measurement object being 25 ° C. Ratio of total content of acidic inorganic salt and monohydrogen phosphate with respect to the total content of inorganic salt in the obtained composition for cold insulation (hereinafter, this value may be indicated by “(X2)”) ), And the ratio of the content of monohydrogen phosphate to the total content of water, inorganic salt and thickener (hereinafter, this value may be indicated by the symbol “(X3)”) is also shown in Table 7. ing.
　次いで、得られた保冷用組成物を高密度ポリエチレン製の容器に封入して、第２実施形態の保冷具を得た。 Next, the obtained cold insulation composition was sealed in a container made of high-density polyethylene to obtain a cold insulation tool of the second embodiment.
＜保冷用組成物の評価＞
　得られた保冷用組成物を、実施例１と同じ方法で評価した。結果を表９に示す。 <Evaluation of composition for cold preservation>
The obtained composition for cold insulation was evaluated in the same manner as in Example 1. The results are shown in Table 9.
＜保冷用組成物及び保冷具（第２実施形態）の製造、保冷用組成物の評価＞
［実施例１５～３３］
　保冷用組成物の配合成分及びその保冷用組成物での含有量を、表３～５に示すとおりとした点以外は、実施例１４と同じ方法で、第２実施形態の保冷用組成物及び保冷具を製造し、保冷用組成物を評価した。保冷用組成物の各物性を表７～８に、評価結果を表９に、それぞれ示す。 <Manufacture of composition for cold preservation and cold insulation tool (second embodiment), evaluation of composition for cold insulation>
[Examples 15 to 33]
The composition for cold insulation of the second embodiment and the composition for cold insulation in the same manner as in Example 14 except that the components of the cold insulation composition and the content in the cold insulation composition were as shown in Tables 3 to 5 A cold insulation tool was manufactured, and the composition for cold insulation was evaluated. The physical properties of the composition for cold preservation are shown in Tables 7 to 8, and the evaluation results are shown in Table 9, respectively.
［実施例３４］
＜保冷用組成物及び保冷具（第３実施形態）の製造＞
　室温（２０～２５℃）下において、水（７９．３５質量部）にＭＲを添加して溶解させ、次いで、さらに塩化アンモニウム（９．７５質量部）及び塩化カリウム（９．７５質量部）添加して溶解させ、次いで、ＣＭＣ（１．１０質量部）を添加して、室温下のままで１時間撹拌して溶解させ、得られた液状物が十分に増粘していることを確認した後、防腐剤（０．０５質量部）を添加して、室温下のままで３０分間撹拌することにより保冷用組成物を得た。このとき、ＭＲの配合量は、得られた保冷用組成物での含有量が８ｐｐｍとなるように調節した。各配合成分及びその保冷用組成物での含有量を表５に示す。 [Example 34]
<Manufacture of a composition for cold preservation and a cold insulation tool (third embodiment)>
At room temperature (20 to 25 ° C.), MR is added and dissolved in water (79.35 parts by mass), and then ammonium chloride (9.75 parts by mass) and potassium chloride (9.75 parts by mass) are added. Then, CMC (1.10 parts by mass) was added and stirred for 1 hour at room temperature to dissolve, and it was confirmed that the obtained liquid was sufficiently thickened. Thereafter, a preservative (0.05 parts by mass) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a composition for cold preservation. At this time, the blending amount of MR was adjusted so that the content in the obtained cold insulation composition was 8 ppm. Table 5 shows the content of each compounding component and its composition for cold storage.
　また、ｐＨ（α１）、ｐＨ（α２）、ｐＨ（α３）、溶媒が水で温度が２５℃である場合のｐＨ指示薬のｐＫａ、保冷用組成物のｐＨ等の物性を表８に示す。ｐＨ（α１）、ｐＨ（α２）、ｐＨ（α３）及び前記ｐＨは、いずれも測定対象物の温度を２５℃として測定した。得られた保冷用組成物における、無機塩の総含有量に対する、酸性の無機塩の含有量の割合（以下、この値を符号「（Ｘ４）」で示すことがある）も表８に示している。 Table 8 shows physical properties such as pH (α1), pH (α2), pH (α3), pH indicator pKa when the solvent is water and the temperature is 25 ° C., and the pH of the composition for cold preservation. The pH (α1), pH (α2), pH (α3) and the pH were all measured with the temperature of the measurement object being 25 ° C. Table 8 also shows the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt in the obtained cold-retaining composition (hereinafter, this value may be indicated by “(X4)”). Yes.
　次いで、得られた保冷用組成物を高密度ポリエチレン製の容器に封入して、第３実施形態の保冷具を得た。 Next, the obtained cold insulation composition was sealed in a container made of high density polyethylene to obtain the cold insulation tool of the third embodiment.
＜保冷用組成物の評価＞
　得られた保冷用組成物を、実施例１と同じ方法で評価した。結果を表９に示す。 <Evaluation of composition for cold preservation>
The obtained composition for cold insulation was evaluated in the same manner as in Example 1. The results are shown in Table 9.
＜保冷用組成物及び保冷具（第３実施形態）の製造、保冷用組成物の評価＞
［実施例３５～３７］
　保冷用組成物の配合成分及びその保冷用組成物での含有量を、表５に示すとおりとした点以外は、実施例３４と同じ方法で、第３実施形態の保冷用組成物及び保冷具を製造し、保冷用組成物を評価した。保冷用組成物の各物性を表８に、評価結果を表９に、それぞれ示す。 <Manufacture of composition for cold preservation and cold insulation tool (third embodiment), evaluation of composition for cold insulation>
[Examples 35 to 37]
The composition for cold insulation and the cold insulation tool of the third embodiment were the same as in Example 34 except that the components of the cold insulation composition and the content in the cold insulation composition were as shown in Table 5. And the composition for cold preservation was evaluated. Table 8 shows the physical properties of the cold insulation composition, and Table 9 shows the evaluation results.
＜保冷用組成物及び保冷具の製造、保冷用組成物の評価＞
［比較例１～９］
　保冷用組成物の配合成分及びその保冷用組成物での含有量を、表５及び６に示すとおりとした点以外は、実施例１と同じ方法で保冷用組成物及び保冷具を製造し、保冷用組成物を評価した。保冷用組成物の各物性を表８に、評価結果を表９に、それぞれ示す。 <Manufacture of composition for cold preservation and cold insulation, evaluation of composition for cold insulation>
[Comparative Examples 1 to 9]
A composition for cold insulation and a cold insulation tool were produced in the same manner as in Example 1 except that the components in the cold insulation composition and the content in the cold insulation composition were as shown in Tables 5 and 6, The composition for cold preservation was evaluated. Table 8 shows the physical properties of the cold insulation composition, and Table 9 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　上記結果から明らかなように、本発明の第１実施形態に係る保冷具（実施例１～１３）、第２実施形態に係る保冷具（実施例１４～３３）、第３実施形態に係る保冷具（実施例３４～３７）においては、いずれも保冷用組成物の凍結時における無機塩の析出に伴い、ｐＨ指示薬の発色の変化を反映して、保冷用組成物はその凍結の前後において色が明瞭に変化し、冷却状態を容易に視認できた。 As is clear from the above results, the cold insulator according to the first embodiment of the present invention (Examples 1 to 13), the cold insulator according to the second embodiment (Examples 14 to 33), and the cold insulator according to the third embodiment. In each of the ingredients (Examples 34 to 37), the composition for cold preservation was colored before and after freezing, reflecting the change in color development of the pH indicator with the precipitation of inorganic salts during freezing of the composition for cold preservation. Changed clearly, and the cooling state could be easily visually confirmed.
　第１実施形態に係る保冷具のうち、特に実施例１～３、８～１１、１３の保冷具においては、保冷用組成物の色変化の完了に要する時間が短く、特に好ましい性状を示した。 Among the cold insulators according to the first embodiment, particularly in the cold insulators of Examples 1 to 3, 8 to 11, and 13, the time required for completing the color change of the cold insulation composition was short, and particularly preferable properties were exhibited. .
　第２実施形態に係る保冷具のうち、特に実施例２２～２７の保冷具においては、保冷用組成物の色変化の完了に要する時間が短く、特に好ましい性状を示した。これは、保冷用組成物がリン酸二水素塩及び中性の無機塩を含有している場合に、このような好ましい性状を示す傾向にあることを示していた。 Among the cold insulators according to the second embodiment, in particular, in the cold insulators of Examples 22 to 27, the time required for completion of the color change of the cold insulation composition was short, and particularly preferable properties were exhibited. This has shown that there exists a tendency which shows such a preferable property, when the composition for cold preservation contains a dihydrogen phosphate salt and a neutral inorganic salt.
　これに対して、比較例１～９の保冷具においては、保冷用組成物が上記の実施例のものとは異なっており、凍結の前後において色の変化が不明瞭であり、冷却状態の視認が困難であるか又は不可能であった。 On the other hand, in the cold insulation tools of Comparative Examples 1 to 9, the cold insulation composition is different from that in the above examples, the color change is unclear before and after freezing, and the cooling state is visually recognized. Was difficult or impossible.
＜保冷用組成物及び保冷具（第１実施形態）の製造、保冷用組成物の評価＞
［実施例３８～４０］
　保冷用組成物の配合成分及びその保冷用組成物での含有量を表１０に示すとおりとした点以外は、実施例１と同じ方法で、第１実施形態の保冷用組成物及び保冷具を製造し、保冷用組成物を評価した。保冷用組成物の各物性を表１１に、評価結果を表１２に、それぞれ示す。 <Manufacture of composition for cold preservation and cold insulation tool (first embodiment), evaluation of composition for cold insulation>
[Examples 38 to 40]
The composition for cold insulation and the cold insulation tool of the first embodiment were the same as in Example 1 except that the composition components of the cold insulation composition and the content in the cold insulation composition were as shown in Table 10. Manufactured and evaluated compositions for cold storage. Table 11 shows the physical properties of the cold insulation composition, and Table 12 shows the evaluation results.
＜保冷用組成物及び保冷具（第２実施形態）の製造、保冷用組成物の評価＞
［実施例４１～４６］
　保冷用組成物の配合成分及びその保冷用組成物での含有量を表１０に示すとおりとした点以外は、実施例１４と同じ方法で、第２実施形態の保冷用組成物及び保冷具を製造し、保冷用組成物を評価した。保冷用組成物の各物性を表１１に、評価結果を表１２に、それぞれ示す。 <Manufacture of composition for cold preservation and cold insulation tool (second embodiment), evaluation of composition for cold insulation>
[Examples 41 to 46]
The composition for cold insulation and the cold insulation tool of the second embodiment were the same as in Example 14, except that the components of the cold insulation composition and the content in the cold insulation composition were as shown in Table 10. Manufactured and evaluated compositions for cold storage. Table 11 shows the physical properties of the cold insulation composition, and Table 12 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　上記のように、本発明の第１実施形態に係る保冷具（実施例３８～４０）、第２実施形態に係る保冷具（実施例４１～４６）においては、いずれも保冷用組成物の凍結時における無機塩の析出に伴い、ｐＨ指示薬の発色の変化を反映して、保冷用組成物はその凍結の前後において色が明瞭に変化し、冷却状態を容易に視認できた。 As described above, in each of the cold insulator according to the first embodiment of the present invention (Examples 38 to 40) and the cold insulator according to the second embodiment (Examples 41 to 46), freezing of the composition for cold insulation is performed. With the precipitation of the inorganic salt at the time, the color of the cold-retaining composition clearly changed before and after freezing, reflecting the change in color of the pH indicator, and the cooling state could be easily visually confirmed.
　本発明は、各種生鮮物用の保冷具として利用可能である。 The present invention can be used as a cold insulator for various fresh foods.

Claims (7)

  1. 　水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、
    　前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸塩と、を含有し、
    　前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸塩の合計含有量の割合が、５～１００質量％であり、
    　前記保冷用組成物が、前記酸性の無機塩として、リン酸二水素塩とリン酸二水素塩以外の無機塩とを含有し、
    　前記ｐＨ指示薬のｐＫａが４．９～８．０であり、
    　前記保冷用組成物は、リン酸塩、リン酸二水素塩及び水以外の含有成分をすべて除去した場合のｐＨ（α１）が、前記ｐＫａに対して、下記式（ｉ）で表される関係を満たすものである、保冷具。
    　ｐＨ指示薬のｐＫａ≦ｐＨ（α１）≦ｐＨ指示薬のｐＫａ＋１．８　・・・・（ｉ）     A cold insulator provided with a cold insulating composition containing water, an inorganic salt, a thickener and a pH indicator,
    The composition for cold preservation contains, as the inorganic salt, an acidic inorganic salt whose aqueous solution is acidic, and a phosphate,
    In the composition for cold preservation, the ratio of the total content of the acidic inorganic salt and phosphate to the total content of the inorganic salt is 5 to 100% by mass,
    The composition for cold preservation contains, as the acidic inorganic salt, an inorganic salt other than dihydrogen phosphate and dihydrogen phosphate,
    The pH indicator has a pKa of 4.9-8.0,
    In the composition for cold preservation, the pH (α1) when all the components other than phosphate, dihydrogen phosphate and water are removed is expressed by the following formula (i) with respect to the pKa. A cooler that meets the requirements.
    pKa of pH indicator ≦ pH (α1) ≦ pKa of pH indicator + 1.8 (i)
  2. 　前記保冷用組成物のｐＨが４．６～８．８である、請求項１に記載の保冷具。 The cold-retaining tool according to claim 1, wherein the cold-retaining composition has a pH of 4.6 to 8.8.
  3. 　前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が、６．０～８．５となるものである、請求項１又は２に記載の保冷具。 3. The cold-retaining composition has a pH (α3) of 6.0 to 8.5 when all the components other than the thickener and water are replaced with water. The cold insulation described.
  4. 　水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、
    　前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩と、リン酸一水素塩と、を含有し、
    　前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩及びリン酸一水素塩の合計含有量の割合が、５～１００質量％であり、
    　前記保冷用組成物において、水、前記無機塩及び増粘剤の総含有量に対する、リン酸一水素塩の含有量の割合が、０．２～５．０質量％であり、
    　前記ｐＨ指示薬のｐＫａが４．９～８．０である、保冷具。     A cold insulator provided with a cold insulating composition containing water, an inorganic salt, a thickener and a pH indicator,
    The composition for cold preservation contains, as the inorganic salt, an acidic inorganic salt whose aqueous solution is acidic, and a monohydrogen phosphate salt,
    In the composition for cold preservation, the ratio of the total content of the acidic inorganic salt and monohydrogen phosphate to the total content of the inorganic salt is 5 to 100% by mass,
    In the composition for cold preservation, the ratio of the content of monohydrogen phosphate to the total content of water, the inorganic salt and the thickener is 0.2 to 5.0% by mass,
    A cold insulator, wherein the pH indicator has a pKa of 4.9 to 8.0.
  5. 　前記保冷用組成物のｐＨが４．７～８．０である、請求項４に記載の保冷具。 The cold insulation tool according to claim 4, wherein the pH of the cold insulation composition is 4.7 to 8.0.
  6. 　前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が、６．０～９．１となるものである、請求項４又は５に記載の保冷具。 6. The cold-retaining composition according to claim 4 or 5, wherein the pH (α3) is 6.0 to 9.1 when all the components other than the thickener and water are replaced with water. The cold insulation described.
  7. 　水、無機塩、増粘剤及びｐＨ指示薬を含有する保冷用組成物を備えた保冷具であって、
    　前記保冷用組成物が、前記無機塩として、その水溶液が酸性を示す酸性の無機塩を含有し、
    　前記保冷用組成物において、前記無機塩の総含有量に対する、前記酸性の無機塩の含有量の割合が、５～１００質量％であり、
    　前記保冷用組成物は、前記無機塩及び水以外の含有成分をすべて水で置換した場合のｐＨ（α２）が７以下となるものであり、
    　前記保冷用組成物は、前記増粘剤及び水以外の含有成分をすべて水で置換した場合のｐＨ（α３）が７以上となるものであり、
    　ｐＨ（α２）及びｐＨ（α３）が、前記ｐＨ指示薬の変色域よりも低いｐＨ、変色域のｐＨ、及び変色域よりも高いｐＨの３つのｐＨ域のうち、互いに異なるｐＨ域の値を示す、保冷具。     A cold insulator provided with a cold insulating composition containing water, an inorganic salt, a thickener and a pH indicator,
    The composition for cold preservation contains an acidic inorganic salt whose aqueous solution is acidic as the inorganic salt,
    In the composition for cold preservation, the ratio of the content of the acidic inorganic salt to the total content of the inorganic salt is 5 to 100% by mass,
    The composition for cold preservation is such that the pH (α2) is 7 or less when all the components other than the inorganic salt and water are replaced with water,
    The composition for cold preservation has a pH (α3) of 7 or more when all components other than the thickener and water are replaced with water,
    pH (α2) and pH (α3) indicate values in different pH ranges among the three pH ranges of pH lower than the color change range of the pH indicator, pH of the color change range, and pH higher than the color change range. , Cooler.
PCT/JP2016/077127 2015-09-18 2016-09-14 Cold insulation tool WO2017047648A1 (en)

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