WO2016068256A1 - Cold insulation tool - Google Patents
Cold insulation tool Download PDFInfo
- Publication number
- WO2016068256A1 WO2016068256A1 PCT/JP2015/080608 JP2015080608W WO2016068256A1 WO 2016068256 A1 WO2016068256 A1 WO 2016068256A1 JP 2015080608 W JP2015080608 W JP 2015080608W WO 2016068256 A1 WO2016068256 A1 WO 2016068256A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cold
- composition
- indicator
- thickener
- inorganic salt
- Prior art date
Links
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
- C09K5/08—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
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).
- 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. 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.
- 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 thickener is a polysaccharide, and the cold-retaining composition is the inorganic
- a cold insulator having a pH (A) of 7.0 or more when all components other than salt and water are replaced with water and satisfying the relationship of the following formula (I). pH indicator pKa ⁇ 0.5 ⁇ pH (A) ⁇ pH indicator pKa + 3.5 (I)
- the pH of the cold-retaining composition may satisfy the relationship of the following formula (II).
- pKa of pH indicator-0.5 ⁇ pH of composition for cold preservation ⁇ pKa of pH indicator + 3.5
- the cold insulation composition has a pH (B) of 5.0 or more and 9.0 or less when all the components other than the thickener and water are replaced with water. But you can.
- the composition for cold insulation has a content of the inorganic salt of 0.5 to 33% by mass, and a content of the thickener of 0.1 to 10% by mass, The pH indicator content may be 1 to 30 ppm.
- the pKa of the pH indicator may be 4.0 or more and 11.8 or less.
- the inorganic salt is hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, hydrogen carbonate, phosphate, alkali metal chloride or alkaline earth metal chloride. It may be one or more selected from the group consisting of
- the thickener may be one or more selected from the group consisting of carboxyalkyl cellulose, guar gum, hydroxyalkyl guar gum, pectin, xanthan gum, tamarind gum, and carrageenan.
- the cold insulator of the present invention can be easily visually confirmed whether the cooling state is the target state.
- the cold-retaining tool 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 thickener is a polysaccharide, and the cold-retaining composition is
- the pH (A) when all the components other than the inorganic salt and water are replaced with water is 7.0 or more and satisfies the relationship of the following formula (I).
- the cold insulator Since the color of the composition for cold insulation reflecting the presence or absence of color development of the pH indicator largely changes before and after freezing, the cold insulator is in a state where the cooling state is intended (a state where the object can be sufficiently cooled). It can be easily visually confirmed whether or not there is. 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.
- pH (A) is the pH of the replacement composition when all the components other than the inorganic salt and water are replaced with water in the cold-retaining composition, and the content (mass%) in the cold-retaining composition ) And the same content (mass%) as that of the inorganic salt-containing water (for example, an aqueous solution of inorganic salt) containing only the inorganic salt.
- the pH (A) is preferably a pH at a temperature at which the pH indicator is dissolved in the composition for cold preservation, and the temperature of the inorganic salt-containing water is any one of 23 to 27 ° C.
- the pH is more preferably, and the pH when the temperature of the inorganic salt-containing water is 25 ° C. is particularly preferable.
- PH (A) is 7.0 or more, preferably 7.05 or more, and more preferably 7.1 or more. Moreover, it is preferable that pH (A) is 12.2 or less, and it is more preferable that it is 11.8 or less.
- this pH (B) is, in other words, The pH of the thickener-containing water (for example, a thickener aqueous solution) containing only the thickener at the same content (mass%) as the content (mass%) in the cold-retaining composition.
- the pH (B) is preferably a pH at a temperature at which the pH indicator is dissolved in the cooling composition, and the temperature of the thickener-containing water is any temperature of 23 to 27 ° C. In this case, the pH is more preferably, and the pH when the temperature of the thickener-containing water is 25 ° C. is particularly preferable.
- the pH (B) is preferably 5.0 or more, and more preferably 6.0 or more. Moreover, it is preferable that pH (B) is 9.0 or less, and it is more preferable that it is 8.2 or less.
- the cold-retaining composition uses a polysaccharide as a thickening agent, and can adjust the acidity of the cold-retaining composition as an inorganic salt, and also affects the color development of the pH indicator.
- a polysaccharide as a thickening agent
- the pH indicator can adjust the acidity of the cold-retaining composition as an inorganic salt, and also affects the color development of the pH indicator.
- aqueous solution having a pH within a specific range
- further combining a pH indicator having a suitable color change range with these thickeners and inorganic salts The color change is remarkably increased.
- each component will be described.
- the said inorganic salt (salt of an inorganic compound) 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. Further, the inorganic salt does not correspond to the pH indicator, and is a component that can be precipitated as crystals or amorphous (amorphous) at the time of freezing the composition for cold insulation, and is involved in the color change of the composition for cold preservation by precipitation. It is possible. As described above, the color of the composition for cold preservation before and after freezing mainly reflects the color at the time of color development of the pH indicator, but the color of the composition for cold preservation after freezing (when frozen) is precipitated. It is somewhat affected by the color of the inorganic salt (usually white).
- the amount of the inorganic salt dissolved before the freezing, preferably in the refrigerated composition at 0 ° C. or higher, is preferably as large as possible.
- 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 of the inorganic salt deposited in the composition for cold preservation after freezing is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably, it may be 100% by mass (total amount).
- the inorganic salt is not particularly limited as long as the pH (A) satisfies the above conditions.
- metal ions in the cation constituting the inorganic salt include alkali metal ions such as lithium ion (Li + ), sodium ion (Na + ), and potassium ion (K + ); magnesium ion (Mg 2+ ), calcium Ions of alkaline earth metals such as ions (Ca 2+ ); ions of transition metals such as iron ions (Fe 3+ , Fe 2+ ), copper ions (Cu 2+ , Cu + ); zinc ions (Zn 2+ ), aluminum ions ( And ions of Group 12 or Group 13 metals such as Al 3+ ).
- the non-metal ion in the cation constituting the inorganic salt include ammonium ion (NH 4 + ) and the like.
- anion constituting the inorganic salt examples include halogen ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodide ion (I ⁇ ); sulfate ion (SO 4 2 ⁇ ); nitrate ion.
- halogen ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodide ion (I ⁇ ); sulfate ion (SO 4 2 ⁇ ); nitrate ion.
- the inorganic salt is not particularly limited.
- alkali metal chlorides such as sodium chloride (NaCl) and potassium chloride (KCl); hydrochlorides such as ammonium chloride (NH 4 Cl); sodium sulfate (Na 2 SO 4 ) , Potassium sulfate (K 2 SO 4 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), magnesium sulfate (MgSO 4 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), nickel sulfate (NiSO 4 ), alum (AlK) Sulfates such as (SO 4 ) 2 ), ammonium alum (Al (NH 4 ) (SO 4 ) 2 ); sodium nitrate (NaNO 3 ), potassium nitrate (KNO 3 ), ammonium nitrate (NH 4 NO 3 ), calcium nitrate four Hydrates (Ca (NO 3 ) 2 .4H 2 O), calcium
- the inorganic salts may be used alone or in combination of two or more.
- the inorganic salts are hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, bicarbonate, phosphate, alkali metal chloride, alkaline earth metal chloride, sulfite, chlorate, One or more selected from the group consisting of perchlorates, thiosulfates, alkali metal bromides, alkali metal iodides and borates are preferred.
- the inorganic salt is selected from the group consisting of hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, hydrogen carbonate, phosphate, alkali metal chloride and alkaline earth metal chloride. It is more preferable that it is 1 type or more. By using such an inorganic salt, the composition for cold preservation has a large color change before and after freezing and is excellent in handleability.
- the inorganic salt is preferably dihydrogen phosphate or hydrogen phosphate in that there are many types of pH indicators that can be used in combination, and the color change of the composition for cold preservation before and after freezing is greater. More preferably, it is a dihydrogen salt.
- the inorganic salt is selected from the group consisting of hydrogen phosphate, carbonate, sulfate, and alkali metal chloride because the color change before and after freezing of the composition for cold preservation becomes larger.
- One or more types are particularly preferred.
- the content of the inorganic salt in the composition for cold preservation is not particularly limited as long as the pH (A) is within a predetermined range, but is preferably 0.5 to 33% by mass, and preferably 1 to 31% by mass. More preferably, for example, it may be 0.5 to 22% by mass, 1 to 19% by mass, or the like.
- the said thickener improves the viscosity of the said composition for cold preservation, is a component which does not correspond to the said pH indicator, and is a polysaccharide in this invention.
- the thickening agent is usually a component that suppresses precipitation both when the cryopreservation composition is not frozen and when it 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.
- the thickener is preferably as less as the amount deposited, 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 may be 0% by mass (the entire amount may not be precipitated).
- the thickener is not particularly limited, and examples thereof include carboxyalkyl cellulose such as carboxymethylcellulose (CMC); guar gum; hydroxyalkyl guar gum such as hydroxypropyl guar gum; pectin; xanthan gum; tamarind gum; .
- the above thickeners may be used alone or in combination of two or more.
- the content of the thickener in the composition for cold preservation is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 0.1 to 10% by mass, and preferably 0.3 to 4% by mass. Is more preferable.
- the pH indicator 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 may be a known one, and is not particularly limited.
- examples include red, methyl purple, phenolphthalein, litmus, p-nitrophenol, chlorophenol red, neutral red, p-naphtholphthalein, cresol red, thymol blue, thymolphthalein and the like.
- the pH indicator preferably has a pKa (acid dissociation constant) of 4.0 or more, and more preferably 5.0 or more. Further, the pH indicator preferably has a pKa of 11.8 or less, more preferably 11.5 or less.
- pKa of the pH indicator in this invention means the value when a solvent is water and temperature is 25 degreeC.
- the pH indicator may be used alone or in combination of two or more, but usually it is preferable to use one alone.
- the content of the pH indicator in the cold-retaining composition 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 more preferably 5 to 20 ppm. .
- the cold-retaining composition satisfies the relationship of the formula (I). That is, the lower limit value of pH (A) is a value smaller by 0.5 than the pKa of the pH indicator, and the upper limit value of pH (A) is a value that is larger by 3.5 than the pKa of the pH indicator. is there.
- the lower limit value of pH (A) is preferably a value that is smaller by 0.3 than the pKa of the pH indicator, and more preferably a value that is smaller by 0.1 than the pKa of the pH indicator.
- the upper limit value of pH (A) is preferably a value that is 3.3 larger than the pKa of the pH indicator, and more preferably a value that is 3.0 larger than the pKa of the pH indicator. By being in such a range, the color change of the composition for cold preservation before and after freezing becomes larger.
- the composition for cold preservation may contain, in addition to water, the inorganic salt, the thickener, and the pH indicator, other components that do not fall within the scope of the effects of the present invention.
- the other components include solvents other than water; various known additives such as preservatives; salts other than inorganic salts (that is, organic salts and salts of organic compounds); thickeners other than polysaccharides, and the like. It is done.
- the solvent is preferably one that can dissolve the inorganic salt, thickener, and pH indicator, and examples of such a solvent include alcohol.
- the said solvent may be used individually by 1 type, and may use 2 or more types together.
- the freezing temperature of the cryogen 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, more preferably 5% by mass or less, and 2% by mass or less. It is particularly preferred that it may be 0% by mass.
- preservative examples include food preservatives and antioxidants, and examples include sodium pyrithione, paraben (paraoxybenzoic acid ester), protamine, and organic nitrogen sulfur compounds. What is necessary is just to adjust suitably content of the said preservative in the composition for cold preservation according to the kind of preservative.
- Examples of the organic salt include organic acid salts and organic base salts.
- Examples of the salt of the organic acid include a salt formed by reacting an acid group of an organic acid such as carboxylic acid or sulfonic acid with an inorganic base or an organic base.
- Examples of the salt of the organic base include salts formed by reacting a group containing a nitrogen atom of a nitrogen-containing organic compound such as a primary amine, secondary amine, and tertiary amine with an inorganic acid or an organic acid.
- the said organic salt may be used individually by 1 type, and may use 2 or more types together.
- the ratio of the content of the organic salt to the total content of the inorganic salt and the organic salt is preferably 5% by mass or less, and preferably 3% by mass or less. More preferably, it is particularly preferably 1% by mass or less, and may be 0% by mass.
- thickeners other than the polysaccharide examples include acrylic polymers such as polyacrylic acid and sodium polyacrylate (polyacrylic acid in which one or more hydrogen atoms may be substituted with groups other than hydrogen atoms and Salt thereof, carboxyvinyl polymer); and alkylene glycols such as propylene glycol.
- Thickeners other than the polysaccharides may be used alone or in combination of two or more. In the present specification, unless otherwise specified, the simple description “thickener” means “thickener that is a polysaccharide”.
- the ratio of the content of the thickener other than the polysaccharide to the total content of the thickener that is the polysaccharide and the other thickener is It is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 2% by mass or less, and may be 0% by mass.
- the composition for cold preservation is composed of the inorganic salt and the polyvalent salt with respect to the total content of components other than water and the solvent (the inorganic salt, the thickener that is a polysaccharide, the pH indicator, and other components other than the solvent).
- the total content ratio of the thickener and the pH indicator, which are saccharides, is preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass. When the ratio of the total content is equal to or more than the lower limit value, the color change of the composition for cold preservation before and after freezing becomes larger.
- the composition for cold preservation has a pH (C) of pH (C) before freezing (when it is not frozen).
- C pH
- pH indicator pKa 0.5 ⁇ pH (C) ⁇ pH indicator pKa + 3.5
- the pH (C) is the pH before freezing (when not frozen) of the cold-retaining composition, preferably the pH at the temperature at which the pH indicator is dissolved in the cold-retaining composition,
- the pH is more preferably when the temperature of the cold-retaining composition is any of 23 to 27 ° C., and the pH is particularly preferably when the temperature of the cold-retaining composition is 25 ° C.
- PH (C) is preferably 5.3 or more, and more preferably 6.4 or more. Moreover, it is preferable that pH (C) is 12.0 or less, and it is more preferable that it is 11.5 or less.
- the composition for cold preservation is preferably such that the lower limit value of pH (C) is 0.5 smaller than the pKa of the pH indicator, and the upper limit value of pH (C) is The value is preferably 3.5 larger than the pKa of the pH indicator.
- the lower limit value of pH (C) is more preferably a value that is smaller by 0.4 than the pKa of the pH indicator, and particularly preferably a value that is smaller by 0.3 than the pKa of the pH indicator.
- the upper limit of pH (C) is more preferably a value that is 3.3 larger than the pKa of the pH indicator, and particularly preferably a value that is 3.0 larger than the pKa of the pH indicator. . By being in such a range, the color change of the composition for cold preservation before and after freezing becomes larger.
- the composition for cold preservation is obtained by blending water, the inorganic salt, the thickener, the pH indicator, and, if necessary, the other components.
- 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-retaining tool of the present invention includes the cold-retaining composition, and is configured by holding the cold-retaining composition by holding means such as a container that can enclose a liquid material.
- the material of the holding means is not particularly limited as long as it is transparent to the extent that the color change (discoloration) of the held cooling composition can be visually recognized.
- Preferred examples include polyethylene and polypropylene. And synthetic resins such as polyamides, polyesters, and the like. Among these, polyolefin is preferable from the viewpoint of excellent low-temperature brittleness resistance, water resistance, chemical resistance, and the like, and high-density polyethylene that is easy to mold and has high strength is more preferable.
- the color-retaining composition 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 can be visually recognized from the outside of the cold insulator, and thereby, it can be easily visually confirmed whether or not the cold insulator is sufficiently cooled to a desired temperature. ing.
- the effect of the cold-retaining composition is not impaired even if cooling and heating are repeated, such as repeated freezing and thawing, the cold-retaining tool provided with the composition is suitable for repeated use. is there.
- the unit “ppm” of the content (blending amount, concentration) of the pH indicator is based on the mass ratio.
- thickeners and pH indicators are shown below.
- Thickener ⁇ CMC (Carboxymethylcellulose): “Serogen” manufactured by Daiichi Kogyo Seiyaku ⁇ GG (Guar gum): “Guapack PF-20” manufactured by Sankisha CVP (carboxy vinyl polymer): “Aronbis AH-305X” manufactured by Toa Gosei Co., Ltd.
- BCP Bromocresol purple (Wako Pure Chemical Industries, Ltd.)
- AYR Alizarin Yellow R (Wako Pure Chemical Industries, Ltd.)
- PR Phenol red (manufactured by Wako Pure Chemical Industries)
- BPB Bromophenol blue (manufactured by Wako Pure Chemical Industries, Ltd.)
- BCG Bromocresol Green (Wako Pure Chemical Industries, Ltd.)
- Example 1 ⁇ Manufacture of composition for cold preservation and cold insulation tool> At room temperature (20 to 25 ° C.), water (97 parts by mass), diammonium hydrogen phosphate (2 parts by mass), CMC (1 part by mass) and BCP were added and mixed to obtain a composition for cold preservation. At this time, the blending amount of BCP was adjusted so that the content in the obtained composition for cold insulation was 10 ppm. Table 1 shows each compounding component other than water and its content (concentration), pH (A), pH (B), and the like. And the pH (C) before freezing of the obtained composition for cold preservation was measured. The results are shown in Table 1. The pH (A), pH (B), and pH (C) were all measured with the temperature of the measurement object being 25 ° C.
- the numerical value described in the unit of “mass%” in the column of inorganic salt indicates the content of the inorganic salt of the composition for cold preservation and the concentration of the aqueous inorganic salt solution at the time of pH (A) measurement.
- the numerical value described in the unit of “mass%” in the column of the thickener indicates the content of the thickener in the composition for cold preservation and the concentration of the thickener aqueous solution at the time of pH (B) measurement. .
- the obtained composition for cold insulation was sealed in a high-density polyethylene container to obtain a cold insulation tool.
- composition for cold insulation evaluation of composition for cold insulation> [Examples 2 to 19, Comparative Examples 1 to 13] A composition for cold insulation and a cold insulation tool were produced in the same manner as in Example 1 except that the components and concentrations of the cold insulation composition were as shown in Tables 1 to 5, and the cold insulation composition was evaluated. The results are shown in Tables 1-5.
- Example 6 For example, in Example 6, four kinds of sodium chloride, potassium chloride, sodium sulfate, and diammonium hydrogen phosphate are used in combination as the inorganic salt, but the content in these cold-retaining compositions and pH (A )
- the concentration in the aqueous solution at the time of measurement is 10% by mass for sodium chloride, 5% by mass for potassium chloride, 2% by mass for sodium sulfate, and 0.1% by mass for diammonium hydrogen phosphate.
- “-” means that the component is not blended, and accordingly, the corresponding pH (A) or pH (B) is not measured.
- the thickener used is a polysaccharide, and the pH (A) is within a predetermined range regardless of the number of types of inorganic salts used.
- the color of the composition for cold preservation clearly changes before and after freezing, reflecting the change in color development of the pH indicator, and the cooling state is easy. It was visible. Examples 1 to 19 all satisfied the relationship of the above formula (II).
- Comparative Examples 1 to 5 since the relationship of the formula (I) is not satisfied, the color change of the composition for cold preservation is unclear before and after freezing, and it is difficult to visually check the cooling state. Or was impossible.
- Comparative Examples 6 to 8 since the pH (A) is outside the predetermined range, the color change of the composition for cold preservation is unclear before and after freezing, and it is difficult to visually check the cooling state. Or it was impossible.
- Comparative Examples 9 to 12 are cases in which the total amount of the thickener was replaced with water (without using the thickener) in the composition for keeping cold of Comparative Examples 1 to 4.
- Comparative Example 13 is a case where an inorganic salt-free refrigeration composition was used, but as with other comparative examples, the color change of the refrigeration composition was unclear before and after freezing, Visibility of the cooling state was difficult or impossible.
- the present invention can be used as a cold insulator for various fresh foods.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Thermotherapy And Cooling Therapy Devices (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Freezing, Cooling And Drying Of Foods (AREA)
Abstract
Description
本願は、2014年10月30日に、日本に出願された特願2014-221679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. 2014-221679 filed in Japan on October 30, 2014, the contents of which are incorporated herein by reference.
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).
pH指示薬のpKa-0.5≦pH(A)≦pH指示薬のpKa+3.5 ・・・・(I) 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 thickener is a polysaccharide, and the cold-retaining composition is the inorganic Provided is a cold insulator having a pH (A) of 7.0 or more when all components other than salt and water are replaced with water and satisfying the relationship of the following formula (I).
pH indicator pKa−0.5 ≦ pH (A) ≦ pH indicator pKa + 3.5 (I)
pH指示薬のpKa-0.5≦保冷用組成物のpH≦pH指示薬のpKa+3.5 ・・・・(II)
本発明の保冷具においては、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(B)が、5.0以上9.0以下であるものでもよい。
本発明の保冷具においては、前記保冷用組成物が、前記無機塩の含有量が0.5~33質量%であり、前記増粘剤の含有量が0.1~10質量%であり、前記pH指示薬の含有量が1~30ppmのものであってもよい。 In the cold insulator of the present invention, the pH of the cold-retaining composition may satisfy the relationship of the following formula (II).
pKa of pH indicator-0.5 ≤ pH of composition for cold preservation ≤ pKa of pH indicator + 3.5 (II)
In the cold insulation tool of the present invention, the cold insulation composition has a pH (B) of 5.0 or more and 9.0 or less when all the components other than the thickener and water are replaced with water. But you can.
In the cold insulation tool of the present invention, the composition for cold insulation has a content of the inorganic salt of 0.5 to 33% by mass, and a content of the thickener of 0.1 to 10% by mass, The pH indicator content may be 1 to 30 ppm.
本発明の保冷具においては、前記無機塩が、塩酸塩、硫酸塩、硝酸塩、炭酸塩、リン酸水素塩、炭酸水素塩、リン酸塩、アルカリ金属の塩化物及びアルカリ土類金属の塩化物からなる群から選択される1種以上であってもよい。
本発明の保冷具においては、前記増粘剤が、カルボキシアルキルセルロース、グアーガム、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、タマリンドガム及びカラギーナンからなる群から選択される1種以上であってもよい。 In the cold insulator of the present invention, the pKa of the pH indicator may be 4.0 or more and 11.8 or less.
In the cold insulator of the present invention, the inorganic salt is hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, hydrogen carbonate, phosphate, alkali metal chloride or alkaline earth metal chloride. It may be one or more selected from the group consisting of
In the cold insulator of the present invention, the thickener may be one or more selected from the group consisting of carboxyalkyl cellulose, guar gum, hydroxyalkyl guar gum, pectin, xanthan gum, tamarind gum, and carrageenan.
pH指示薬のpKa-0.5≦pH(A)≦pH指示薬のpKa+3.5 ・・・・(I) The cold-retaining tool 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 thickener is a polysaccharide, and the cold-retaining composition is The pH (A) when all the components other than the inorganic salt and water are replaced with water is 7.0 or more and satisfies the relationship of the following formula (I).
pH indicator pKa−0.5 ≦ pH (A) ≦ pH indicator pKa + 3.5 (I)
pH(A)は、前記pH指示薬が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、前記無機塩含有水の温度が23~27℃のいずれかの温度である場合のpHであることがより好ましく、前記無機塩含有水の温度が25℃である場合のpHであることが特に好ましい。 pH (A) is the pH of the replacement composition when all the components other than the inorganic salt and water are replaced with water in the cold-retaining composition, and the content (mass%) in the cold-retaining composition ) And the same content (mass%) as that of the inorganic salt-containing water (for example, an aqueous solution of inorganic salt) containing only the inorganic salt.
The pH (A) is preferably a pH at a temperature at which the pH indicator is dissolved in the composition for cold preservation, and the temperature of the inorganic salt-containing water is any one of 23 to 27 ° C. The pH is more preferably, and the pH when the temperature of the inorganic salt-containing water is 25 ° C. is particularly preferable.
pH(B)は、前記pH指示薬が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、前記増粘剤含有水の温度が23~27℃のいずれかの温度である場合のpHであることがより好ましく、前記増粘剤含有水の温度が25℃である場合のpHであることが特に好ましい。 In the cold-retaining composition, when the pH of the replacement composition when all the components other than the thickener and water are replaced with water is “pH (B)”, this pH (B) is, in other words, The pH of the thickener-containing water (for example, a thickener aqueous solution) containing only the thickener at the same content (mass%) as the content (mass%) in the cold-retaining composition.
The pH (B) is preferably a pH at a temperature at which the pH indicator is dissolved in the cooling composition, and the temperature of the thickener-containing water is any temperature of 23 to 27 ° C. In this case, the pH is more preferably, and the pH when the temperature of the thickener-containing water is 25 ° C. is particularly preferable.
以下、各成分について説明する。 The cold-retaining composition uses a polysaccharide as a thickening agent, and can adjust the acidity of the cold-retaining composition as an inorganic salt, and also affects the color development of the pH indicator. Depending on the change or presence or absence of color development of the pH indicator by using an aqueous solution having a pH within a specific range, and further combining a pH indicator having a suitable color change range with these thickeners and inorganic salts. The color change is remarkably increased.
Hereinafter, each component will be described.
また、前記無機塩は、前記pH指示薬に該当せず、保冷用組成物の凍結時に、結晶又はアモルファス(非晶質)として析出し得る成分であり、析出によって保冷用組成物の色変化に関与し得るものである。凍結の前後における保冷用組成物の色は、上述のように、pH指示薬の発色時の色が主として反映されたものであるが、凍結後(凍結時)の保冷用組成物の色は、析出した無機塩の色(通常は白色)の影響を多少受ける。 The said inorganic salt (salt of an inorganic compound) 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.
Further, the inorganic salt does not correspond to the pH indicator, and is a component that can be precipitated as crystals or amorphous (amorphous) at the time of freezing the composition for cold insulation, and is involved in the color change of the composition for cold preservation by precipitation. It is possible. As described above, the color of the composition for cold preservation before and after freezing mainly reflects the color at the time of color development of the pH indicator, but the color of the composition for cold preservation after freezing (when frozen) is precipitated. It is somewhat affected by the color of the inorganic salt (usually white).
また、前記無機塩は、凍結後の保冷用組成物中で、その析出している量が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。 The amount of the inorganic salt dissolved before the freezing, preferably in the refrigerated composition at 0 ° C. or higher, is preferably as large as possible. 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).
Further, the amount of the inorganic salt deposited in the composition for cold preservation after freezing is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably, it may be 100% by mass (total amount).
前記無機塩を構成するカチオンで金属イオンとしては、例えば、リチウムイオン(Li+)、ナトリウムイオン(Na+)、カリウムイオン(K+)等のアルカリ金属のイオン;マグネシウムイオン(Mg2+)、カルシウムイオン(Ca2+)等のアルカリ土類金属のイオン;鉄イオン(Fe3+、Fe2+)、銅イオン(Cu2+、Cu+)等の遷移金属のイオン;亜鉛イオン(Zn2+)、アルミニウムイオン(Al3+)等の第12族又は第13族の金属のイオン等が挙げられる。
前記無機塩を構成するカチオンで非金属イオンとしては、例えば、アンモニウムイオン(NH4 +)等が挙げられる。 The inorganic salt is not particularly limited as long as the pH (A) satisfies the above conditions.
Examples of metal ions in the cation constituting the inorganic salt include alkali metal ions such as lithium ion (Li + ), sodium ion (Na + ), and potassium ion (K + ); magnesium ion (Mg 2+ ), calcium Ions of alkaline earth metals such as ions (Ca 2+ ); ions of transition metals such as iron ions (Fe 3+ , Fe 2+ ), copper ions (Cu 2+ , Cu + ); zinc ions (Zn 2+ ), aluminum ions ( And ions of Group 12 or Group 13 metals such as Al 3+ ).
Examples of the non-metal ion in the cation constituting the inorganic salt include ammonium ion (NH 4 + ) and the like.
そして、前記無機塩は、塩酸塩、硫酸塩、硝酸塩、炭酸塩、リン酸水素塩、炭酸水素塩、リン酸塩、アルカリ金属の塩化物及びアルカリ土類金属の塩化物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。
このような無機塩を用いることで、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 inorganic salts are hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, bicarbonate, phosphate, alkali metal chloride, alkaline earth metal chloride, sulfite, chlorate, One or more selected from the group consisting of perchlorates, thiosulfates, alkali metal bromides, alkali metal iodides and borates are preferred.
The inorganic salt is selected from the group consisting of hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, hydrogen carbonate, phosphate, alkali metal chloride and alkaline earth metal chloride. It is more preferable that it is 1 type or more.
By using such an inorganic salt, the composition for cold preservation has a large color change before and after freezing and is excellent in handleability.
前記増粘剤は、通常、前記保冷用組成物の非凍結時及び凍結時のいずれにおいても析出が抑制される成分である。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。 The said thickener improves the viscosity of the said composition for cold preservation, is a component which does not correspond to the said pH indicator, and is a polysaccharide in this invention.
The thickening agent is usually a component that suppresses precipitation both when the cryopreservation composition is not frozen and when it 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.
なお、本発明における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 preferably has a pKa (acid dissociation constant) of 4.0 or more, and more preferably 5.0 or more. Further, the pH indicator preferably has a pKa of 11.8 or less, more preferably 11.5 or less.
In addition, unless otherwise indicated, pKa of the pH indicator in this invention means the value when a solvent is water and temperature is 25 degreeC.
そして、pH(A)の下限値は、前記pH指示薬のpKaよりも0.3だけ小さい値であることが好ましく、前記pH指示薬のpKaよりも0.1だけ小さい値であることがより好ましい。また、pH(A)の上限値は、前記pH指示薬のpKaよりも3.3だけ大きい値であることが好ましく、前記pH指示薬のpKaよりも3.0だけ大きい値であることがより好ましい。このような範囲であることで、凍結の前後における保冷用組成物の色変化がより大きくなる。 The cold-retaining composition satisfies the relationship of the formula (I). That is, the lower limit value of pH (A) is a value smaller by 0.5 than the pKa of the pH indicator, and the upper limit value of pH (A) is a value that is larger by 3.5 than the pKa of the pH indicator. is there.
The lower limit value of pH (A) is preferably a value that is smaller by 0.3 than the pKa of the pH indicator, and more preferably a value that is smaller by 0.1 than the pKa of the pH indicator. Further, the upper limit value of pH (A) is preferably a value that is 3.3 larger than the pKa of the pH indicator, and more preferably a value that is 3.0 larger than the pKa of the pH indicator. By being in such a range, the color change of the composition for cold preservation before and after freezing becomes larger.
前記溶媒は1種を単独で用いてもよいし、2種以上を併用してもよい。 The solvent is preferably one that can dissolve the inorganic salt, thickener, and pH indicator, and examples of such a solvent include alcohol.
The said solvent may be used individually by 1 type, and may use 2 or more types together.
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く、0質量%であってもよい。 Water and the solvent function as one component of a cryogen, and together with the inorganic salt, the freezing temperature of the cryogen composition is determined mainly by the type and amount thereof.
In the composition for cold preservation, the ratio of the content of the solvent to the total content of water and the solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass or less. It is particularly preferred that it may be 0% by mass.
保冷用組成物における前記防腐剤の含有量は、防腐剤の種類に応じて適宜調節すればよい。 Examples of the preservative include food preservatives and antioxidants, and examples include sodium pyrithione, paraben (paraoxybenzoic acid ester), protamine, and organic nitrogen sulfur compounds.
What is necessary is just to adjust suitably content of the said preservative in the composition for cold preservation according to the kind of preservative.
前記有機酸の塩としては、例えば、カルボン酸、スルホン酸等の有機酸の酸基が、無機塩基又は有機塩基と反応してなる塩が挙げられる。
前記有機塩基の塩としては、例えば、第1級アミン、第2級アミン、第3級アミン等の含窒素有機化合物の窒素原子を含む基が、無機酸又は有機酸と反応してなる塩が挙げられる。
前記有機塩は、1種を単独で用いてもよいし、2種以上を併用してもよい。 Examples of the organic salt include organic acid salts and organic base salts.
Examples of the salt of the organic acid include a salt formed by reacting an acid group of an organic acid such as carboxylic acid or sulfonic acid with an inorganic base or an organic base.
Examples of the salt of the organic base include salts formed by reacting a group containing a nitrogen atom of a nitrogen-containing organic compound such as a primary amine, secondary amine, and tertiary amine with an inorganic acid or an organic acid. Can be mentioned.
The said organic salt may be used individually by 1 type, and may use 2 or more types together.
前記多糖類以外の増粘剤は、1種を単独で用いてもよいし、2種以上を併用してもよい。
なお、本明細書においては、特に断りのない限り、単なる「増粘剤」との記載は、「多糖類である増粘剤」を意味するものとする。 Examples of thickeners other than the polysaccharide include acrylic polymers such as polyacrylic acid and sodium polyacrylate (polyacrylic acid in which one or more hydrogen atoms may be substituted with groups other than hydrogen atoms and Salt thereof, carboxyvinyl polymer); and alkylene glycols such as propylene glycol.
Thickeners other than the polysaccharides may be used alone or in combination of two or more.
In the present specification, unless otherwise specified, the simple description “thickener” means “thickener that is a polysaccharide”.
pH指示薬のpKa-0.5≦pH(C)≦pH指示薬のpKa+3.5 ・・・・(II) From the point that the color change of the composition for cold preservation before and after freezing becomes larger, the composition for cold preservation has a pH (C) of pH (C) before freezing (when it is not frozen). Those satisfying the relationship of the following formula (II) are preferable.
pH indicator pKa−0.5 ≦ pH (C) ≦ pH indicator pKa + 3.5 (II)
そして、pH(C)の下限値は、前記pH指示薬のpKaよりも0.4だけ小さい値であることがより好ましく、前記pH指示薬のpKaよりも0.3だけ小さい値であることが特に好ましい。また、pH(C)の上限値は、前記pH指示薬のpKaよりも3.3だけ大きい値であることがより好ましく、前記pH指示薬のpKaよりも3.0だけ大きい値であることが特に好ましい。このような範囲であることで、凍結の前後における保冷用組成物の色変化がより大きくなる。 As described above, the composition for cold preservation is preferably such that the lower limit value of pH (C) is 0.5 smaller than the pKa of the pH indicator, and the upper limit value of pH (C) is The value is preferably 3.5 larger than the pKa of the pH indicator.
The lower limit value of pH (C) is more preferably a value that is smaller by 0.4 than the pKa of the pH indicator, and particularly preferably a value that is smaller by 0.3 than the pKa of the pH indicator. . The upper limit of pH (C) is more preferably a value that is 3.3 larger than the pKa of the pH indicator, and particularly preferably a value that is 3.0 larger than the pKa of the pH indicator. . By being in such a range, the color change of the composition for cold preservation before and after freezing becomes larger.
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 is obtained by blending water, the inorganic salt, the thickener, the pH indicator, and, if necessary, the other components.
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.
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、特に限定されず、好ましいものとしては、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が挙げられる。これらの中でも、耐低温脆性、耐水性及び耐薬品性等に優れる点から、ポリオレフィンが好ましく、成形が容易で、高い強度を有する高密度ポリエチレンがより好ましい。 The cold-retaining tool of the present invention includes the cold-retaining composition, and is configured by holding the cold-retaining composition by holding means such as a container that can enclose a liquid material.
The material of the holding means is not particularly limited as long as it is transparent to the extent that the color change (discoloration) of the held cooling composition can be visually recognized. Preferred examples include polyethylene and polypropylene. And synthetic resins such as polyamides, polyesters, and the like. Among these, polyolefin is preferable from the viewpoint of excellent low-temperature brittleness resistance, water resistance, chemical resistance, and the like, and high-density polyethylene that is easy to mold and has high strength is more preferable.
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無いので、これを備えた保冷具は、繰り返し利用にも適したものである。 Since the color-retaining composition 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 can be visually recognized from the outside of the cold insulator, and thereby, it can be easily visually confirmed whether or not the cold insulator is sufficiently cooled to a desired temperature. ing.
In addition, since the effect of the cold-retaining composition is not impaired even if cooling and heating are repeated, such as repeated freezing and thawing, the cold-retaining tool provided with the composition is suitable for repeated use. is there.
(増粘剤)
・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」
・GG(グアーガム):三晶社製「グアパックPF-20」
・CVP(カルボキシビニルポリマー):東亜合成社製「アロンビスAH-305X」
(pH指示薬)
・BCP:ブロモクレゾールパープル(和光純薬社製)
・AYR:アリザリンイエローR(和光純薬社製)
・PR:フェノールレッド(和光純薬社製)
・BPB:ブロモフェノールブルー(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) Of the raw materials used in the examples and comparative examples, thickeners and pH indicators are shown below.
(Thickener)
・ CMC (Carboxymethylcellulose): “Serogen” manufactured by Daiichi Kogyo Seiyaku
・ GG (Guar gum): “Guapack PF-20” manufactured by Sankisha
CVP (carboxy vinyl polymer): “Aronbis AH-305X” manufactured by Toa Gosei Co., Ltd.
(PH indicator)
・ BCP: Bromocresol purple (Wako Pure Chemical Industries, Ltd.)
・ AYR: Alizarin Yellow R (Wako Pure Chemical Industries, Ltd.)
・ PR: Phenol red (manufactured by Wako Pure Chemical Industries)
・ BPB: Bromophenol blue (manufactured by Wako Pure Chemical Industries, Ltd.)
・ BCG: Bromocresol Green (Wako Pure Chemical Industries, Ltd.)
<保冷用組成物及び保冷具の製造>
室温(20~25℃)において、水(97質量部)、リン酸水素二アンモニウム(2質量部)、CMC(1質量部)、BCPを添加及び混合して、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10ppmとなるように調節した。水以外の各配合成分及びその含有量(濃度)、pH(A)並びにpH(B)等を表1に示す。そして、得られた保冷用組成物の凍結前のpH(C)を測定した。結果を表1に示す。pH(A)、pH(B)及びpH(C)は、すべて測定対象物の温度を25℃として測定した。
なお、表1において、無機塩の欄に「質量%」単位で記載されている数値は、保冷用組成物の無機塩の含有量、及びpH(A)測定時の無機塩水溶液の濃度を示す。同様に、増粘剤の欄に「質量%」単位で記載されている数値は、保冷用組成物の増粘剤の含有量、及びpH(B)測定時の増粘剤水溶液の濃度を示す。これは、以降の表においても同様である。
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、保冷具を得た。 [Example 1]
<Manufacture of composition for cold preservation and cold insulation tool>
At room temperature (20 to 25 ° C.), water (97 parts by mass), diammonium hydrogen phosphate (2 parts by mass), CMC (1 part by mass) and BCP were added and mixed to obtain a composition for cold preservation. At this time, the blending amount of BCP was adjusted so that the content in the obtained composition for cold insulation was 10 ppm. Table 1 shows each compounding component other than water and its content (concentration), pH (A), pH (B), and the like. And the pH (C) before freezing of the obtained composition for cold preservation was measured. The results are shown in Table 1. The pH (A), pH (B), and pH (C) were all measured with the temperature of the measurement object being 25 ° C.
In Table 1, the numerical value described in the unit of “mass%” in the column of inorganic salt indicates the content of the inorganic salt of the composition for cold preservation and the concentration of the aqueous inorganic salt solution at the time of pH (A) measurement. . Similarly, the numerical value described in the unit of “mass%” in the column of the thickener indicates the content of the thickener in the composition for cold preservation and the concentration of the thickener aqueous solution at the time of pH (B) measurement. . The same applies to the following tables.
Next, the obtained composition for cold insulation was sealed in a high-density polyethylene container to obtain a cold insulation tool.
(色変化)
得られた保冷用組成物(保冷具)を-25℃まで冷却し、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1に示す。
なお、表1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、「青紫→黄」とは、保冷用組成物の色が凍結前は青紫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。 <Evaluation of composition for cold preservation>
(Color change)
The obtained cold insulation composition (cold insulation device) was cooled to −25 ° C., and the color change of the cold insulation composition before and after freezing was visually evaluated according to the following criteria. The results are shown in Table 1.
In Table 1, “color change” described in the column of the evaluation result indicates a color change of the composition for cold preservation before and after freezing. For example, “blue purple → yellow” means a composition for cold preservation. Indicates that the color was blue-purple 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.
[実施例2~19、比較例1~13]
保冷用組成物の配合成分及び濃度を表1~5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。結果を表1~5に示す。例えば、実施例6では、無機塩として、塩化ナトリウム、塩化カリウム、硫酸ナトリウム及びリン酸水素二アンモニウムの4種を併用しているが、これらの保冷用組成物での含有量、及びpH(A)測定時の水溶液での濃度は、塩化ナトリウムが10質量%、塩化カリウムが5質量%、硫酸ナトリウムが2質量%、リン酸水素二アンモニウムが0.1質量%である。なお、表中、「-」は、その成分が未配合であり、それに伴い、対応するpH(A)又はpH(B)も未測定であることを意味する。 <Manufacture of composition for cold preservation and cold insulation, evaluation of composition for cold insulation>
[Examples 2 to 19, Comparative Examples 1 to 13]
A composition for cold insulation and a cold insulation tool were produced in the same manner as in Example 1 except that the components and concentrations of the cold insulation composition were as shown in Tables 1 to 5, and the cold insulation composition was evaluated. The results are shown in Tables 1-5. For example, in Example 6, four kinds of sodium chloride, potassium chloride, sodium sulfate, and diammonium hydrogen phosphate are used in combination as the inorganic salt, but the content in these cold-retaining compositions and pH (A ) The concentration in the aqueous solution at the time of measurement is 10% by mass for sodium chloride, 5% by mass for potassium chloride, 2% by mass for sodium sulfate, and 0.1% by mass for diammonium hydrogen phosphate. In the table, “-” means that the component is not blended, and accordingly, the corresponding pH (A) or pH (B) is not measured.
Claims (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、
前記増粘剤は多糖類であり、
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(A)が、7.0以上であり、かつ下記式(I)の関係を満たす、保冷具。
pH指示薬のpKa-0.5≦pH(A)≦pH指示薬のpKa+3.5 ・・・・(I) A cold insulator provided with a cold insulating composition containing water, an inorganic salt, a thickener and a pH indicator,
The thickener is a polysaccharide;
The cold insulation composition has a pH (A) of 7.0 or more and satisfies the relationship of the following formula (I) when all the components other than the inorganic salt and water are replaced with water. .
pH indicator pKa−0.5 ≦ pH (A) ≦ pH indicator pKa + 3.5 (I) - 前記保冷用組成物のpHが、下記式(II)の関係を満たす、請求項1に記載の保冷具。
pH指示薬のpKa-0.5≦保冷用組成物のpH≦pH指示薬のpKa+3.5 ・・・・(II) The cold-retaining tool according to claim 1, wherein a pH of the cold-retaining composition satisfies a relationship represented by the following formula (II).
pKa of pH indicator-0.5 ≤ pH of composition for cold preservation ≤ pKa of pH indicator + 3.5 (II) - 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(B)が、5.0以上9.0以下である、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 (B) of 5.0 or more and 9.0 or less when all the components other than the thickener and water are replaced with water. .
- 前記保冷用組成物が、前記無機塩の含有量が0.5~33質量%であり、前記増粘剤の含有量が0.1~10質量%であり、前記pH指示薬の含有量が1~30ppmのものである、請求項1に記載の保冷具。 In the cold-retaining composition, the content of the inorganic salt is 0.5 to 33% by mass, the content of the thickener is 0.1 to 10% by mass, and the content of the pH indicator is 1 The cold insulator according to claim 1, which is of -30 ppm.
- 前記pH指示薬のpKaが4.0以上11.8以下である、請求項1に記載の保冷具。 The cold insulator according to claim 1, wherein the pH indicator has a pKa of 4.0 or more and 11.8 or less.
- 前記無機塩が、塩酸塩、硫酸塩、硝酸塩、炭酸塩、リン酸水素塩、炭酸水素塩、リン酸塩、アルカリ金属の塩化物及びアルカリ土類金属の塩化物からなる群から選択される1種以上である、請求項1に記載の保冷具。 The inorganic salt is selected from the group consisting of hydrochloride, sulfate, nitrate, carbonate, hydrogen phosphate, bicarbonate, phosphate, alkali metal chloride and alkaline earth metal chloride 1 The cold insulator according to claim 1, wherein the cold insulator is a seed or more.
- 前記増粘剤が、カルボキシアルキルセルロース、グアーガム、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、タマリンドガム及びカラギーナンからなる群から選択される1種以上である、請求項1に記載の保冷具。 The cold insulator according to claim 1, wherein the thickener is at least one selected from the group consisting of carboxyalkyl cellulose, guar gum, hydroxyalkyl guar gum, pectin, xanthan gum, tamarind gum and carrageenan.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016556637A JP6587108B2 (en) | 2014-10-30 | 2015-10-29 | Cooler |
MYPI2017701163A MY183391A (en) | 2014-10-30 | 2015-10-29 | Refrigerant pack |
CN201580058376.0A CN107075354A (en) | 2014-10-30 | 2015-10-29 | Cold insulation utensil |
SG11201702523PA SG11201702523PA (en) | 2014-10-30 | 2015-10-29 | Refrigerant pack |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-221679 | 2014-10-30 | ||
JP2014221679 | 2014-10-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016068256A1 true WO2016068256A1 (en) | 2016-05-06 |
Family
ID=55857591
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/080608 WO2016068256A1 (en) | 2014-10-30 | 2015-10-29 | Cold insulation tool |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6587108B2 (en) |
CN (1) | CN107075354A (en) |
MY (1) | MY183391A (en) |
SG (1) | SG11201702523PA (en) |
WO (1) | WO2016068256A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018016585A1 (en) * | 2016-07-22 | 2018-01-25 | トッパン・フォームズ株式会社 | Cooling tool |
KR20180122570A (en) * | 2018-10-26 | 2018-11-13 | 이재석 | Packing box for cold insulation |
WO2022004322A1 (en) | 2020-06-30 | 2022-01-06 | 株式会社カネカ | Low-temperature transport device and production method therefor, and use thereof |
WO2022172796A1 (en) | 2021-02-10 | 2022-08-18 | 株式会社カネカ | Constant temperature transport container, and constant temperature transport container assembly |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6446754B2 (en) * | 2015-01-20 | 2019-01-09 | トッパン・フォームズ株式会社 | Cooler |
JP6765897B2 (en) * | 2015-09-18 | 2020-10-07 | トッパン・フォームズ株式会社 | Cold storage |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6260435B2 (en) * | 1977-05-02 | 1987-12-16 | Akzo Nv | |
WO2014050157A1 (en) * | 2012-09-28 | 2014-04-03 | トッパン・フォームズ株式会社 | Cooling tool |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7704765A (en) * | 1977-05-02 | 1978-11-06 | Akzo Nv | TEMPERATURE INDICATOR. |
US6656380B2 (en) * | 2001-10-16 | 2003-12-02 | Supachill Technologies Pty. Ltd. | Super-coolable composition having long-duration phase change capability, process for preparation of same, process for super-cooling same and articles comprising same |
UA91791C2 (en) * | 2009-06-04 | 2010-08-25 | Пётр Владиславович Щокин | Continuous flow solar-heat collector |
JP6500312B2 (en) * | 2014-03-20 | 2019-04-17 | トッパン・フォームズ株式会社 | Cooler |
-
2015
- 2015-10-29 MY MYPI2017701163A patent/MY183391A/en unknown
- 2015-10-29 WO PCT/JP2015/080608 patent/WO2016068256A1/en active Application Filing
- 2015-10-29 SG SG11201702523PA patent/SG11201702523PA/en unknown
- 2015-10-29 CN CN201580058376.0A patent/CN107075354A/en active Pending
- 2015-10-29 JP JP2016556637A patent/JP6587108B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6260435B2 (en) * | 1977-05-02 | 1987-12-16 | Akzo Nv | |
WO2014050157A1 (en) * | 2012-09-28 | 2014-04-03 | トッパン・フォームズ株式会社 | Cooling tool |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018016585A1 (en) * | 2016-07-22 | 2018-01-25 | トッパン・フォームズ株式会社 | Cooling tool |
JP2018012812A (en) * | 2016-07-22 | 2018-01-25 | トッパン・フォームズ株式会社 | Cold insulation tool |
KR20180122570A (en) * | 2018-10-26 | 2018-11-13 | 이재석 | Packing box for cold insulation |
KR102070653B1 (en) * | 2018-10-26 | 2020-01-29 | 이재석 | Packing box for cold insulation |
WO2022004322A1 (en) | 2020-06-30 | 2022-01-06 | 株式会社カネカ | Low-temperature transport device and production method therefor, and use thereof |
WO2022172796A1 (en) | 2021-02-10 | 2022-08-18 | 株式会社カネカ | Constant temperature transport container, and constant temperature transport container assembly |
Also Published As
Publication number | Publication date |
---|---|
SG11201702523PA (en) | 2017-05-30 |
JPWO2016068256A1 (en) | 2017-09-28 |
CN107075354A (en) | 2017-08-18 |
MY183391A (en) | 2021-02-18 |
JP6587108B2 (en) | 2019-10-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6587108B2 (en) | Cooler | |
TWI639804B (en) | Refrigerant | |
JP5970318B2 (en) | Cooler | |
JP6360702B2 (en) | Cooler | |
WO2014050158A1 (en) | Cooling tool | |
JP6219653B2 (en) | Cooler | |
JP6650363B2 (en) | Cooler | |
JP6765897B2 (en) | Cold storage | |
JP6446754B2 (en) | Cooler | |
JP6519777B2 (en) | Cooler | |
JP6267554B2 (en) | Cooler | |
JP6278778B2 (en) | Cooler | |
JP2015067648A (en) | Cold insulation tool | |
JP2017179298A (en) | Cold insulation tool | |
JP6088877B2 (en) | Cooler | |
TWI632335B (en) | Cooling pack | |
JP2015063637A (en) | Cold-insulation tool | |
JP2017052953A (en) | Cold insulation tool |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15853721 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016556637 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11201702523P Country of ref document: SG |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15853721 Country of ref document: EP Kind code of ref document: A1 |