WO2015008792A1 - 酸素検知剤組成物、酸素検知シート、脱酸素剤用包装材料、及び脱酸素剤包装体 - Google Patents
酸素検知剤組成物、酸素検知シート、脱酸素剤用包装材料、及び脱酸素剤包装体 Download PDFInfo
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- WO2015008792A1 WO2015008792A1 PCT/JP2014/068913 JP2014068913W WO2015008792A1 WO 2015008792 A1 WO2015008792 A1 WO 2015008792A1 JP 2014068913 W JP2014068913 W JP 2014068913W WO 2015008792 A1 WO2015008792 A1 WO 2015008792A1
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- oxygen
- composition
- oxygen detector
- basic substance
- polyethylene glycol
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
- G01N31/225—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for oxygen, e.g. including dissolved oxygen
Definitions
- the present invention relates to an oxygen detector composition, an oxygen detector sheet, a packaging material for oxygen absorber, and an oxygen absorber package.
- oxygen detectors using organic dyes that change color reversibly by oxidation-reduction reactions have been used.
- a commercially available oxygen detector for example, trade name “AGELESS I”, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- An oxygen scavenger for example, trade name “AGELESS”, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Patent Document 1 discloses an oxygen indicator label containing ethylene glycol.
- Patent Document 2 discloses an oxygen indicator obtained by imparting a polyethylene powder sintered body with a drug having an oxygen sensing ability, including polyethylene glycol.
- Patent Document 3 discloses a method for producing an oxygen detector in which an absorbent capable of impregnating a liquid is impregnated with an oxygen detection solution containing polyethylene glycol.
- Patent Document 4 discloses an oxygen detector composition containing polyethylene glycol.
- Japanese Patent Laid-Open No. 04-151555 Japanese Patent Laid-Open No. 02-057975 JP 2007-298315 A Japanese Patent Laid-Open No. 05-312799
- the oxygen detector composition described in Patent Document 1 exhibits a pink color when the oxygen concentration is less than 0.1% by volume. However, when stored for a long time at room temperature (for example, about 25 to 40 ° C.), It may turn brown. In order to avoid this, when the oxygen detector composition is stored for a long period of time, it is necessary to manage the storage temperature at a low temperature of 15 ° C. or lower. In addition, in the oxygen detector compositions described in Patent Documents 2 to 4, depending on the average molecular weight and blending amount of polyethylene glycol used together, the solubility of basic substances in water, etc., the oxygen detector may be stored at room temperature for a long period of time.
- the present invention has been made in view of the above circumstances, and is an oxygen detector composition that has good responsiveness to changes in oxygen concentration and excellent color retention and printability even when stored at room temperature for a long period of time.
- the purpose is to provide goods.
- the present inventors surprisingly found that the content of polyethylene glycol in the oxygen detector composition containing polyethylene glycol, redox dye, reducing agent and basic substance was reduced.
- a basic substance with a specific ratio and low solubility in water even when stored at room temperature for a long period of time, the responsiveness to changes in oxygen concentration is good, and color retention and It has been found that an oxygen detector composition having excellent printability can be obtained, and has led to the present invention.
- the present invention is as follows.
- An oxygen detector composition comprising polyethylene glycol, a redox dye, a reducing agent and a basic substance,
- the polyethylene glycol content is 5 to 35 mass% with respect to the total amount of the oxygen detector composition
- the basic substance is a poorly water-soluble basic substance having a solubility in water at 20 ° C. of less than 1 g / 100 g-H 2 O;
- ⁇ 3> The oxygen detector composition according to ⁇ 1> or ⁇ 2>, wherein the basic substance is an alkaline earth metal hydroxide, an alkaline earth metal carbonate, or both.
- ⁇ 4> ⁇ 1> to ⁇ 3, wherein the content of the water-soluble basic substance having a solubility in water at 20 ° C. of 1 g / 100 g-H 2 O or more in the oxygen detector composition is 1% by mass or less.
- > The oxygen detector composition according to any one of the above.
- An oxygen detection sheet comprising the oxygen detector composition according to any one of ⁇ 1> to ⁇ 4>.
- ⁇ 6> A packaging material for oxygen scavenger containing the oxygen detection sheet according to ⁇ 5>.
- An oxygen scavenger composition An oxygen scavenger composition; Packaging the oxygen scavenger composition, the packaging material for oxygen scavenger according to ⁇ 6>, An oxygen scavenger package.
- an oxygen detector composition that is excellent in responsiveness to changes in oxygen concentration and excellent in color retention and printability even when stored at room temperature for a long period of time.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
- the oxygen detector composition of this embodiment is an oxygen detector composition containing polyethylene glycol, a redox dye, a reducing agent, and a basic substance, and the content of polyethylene glycol is equal to the total amount of the oxygen detector composition.
- the basic substance is a hardly water-soluble basic substance having a solubility in water at 20 ° C. of less than 1 g / 100 g-H 2 O, and substantially contains trisodium phosphate.
- the oxygen detector composition of the present embodiment has good responsiveness to changes in oxygen concentration and excellent color retention and printability even when stored at room temperature for a long period of time. Further, even when stored at a low temperature, it is a matter of course that the responsiveness to changes in oxygen concentration is good and the color retention and printability are excellent.
- the normal temperature here is about 25 to 40 ° C.
- the oxygen detector composition of this embodiment uses polyethylene glycol as a water retention agent.
- the content of polyethylene glycol in the oxygen detector composition is 5 to 35% by mass.
- the content of polyethylene glycol is preferably 10 to 30% by mass, and more preferably 12 to 20% by mass.
- the average molecular weight of polyethylene glycol is not particularly limited, but is preferably 200 to 2000, more preferably 200 to 1000, still more preferably 200 to 700, and even more preferably 300 to 600. preferable.
- the average molecular weight of polyethylene glycol in the present specification refers to the average molecular weight determined by the macrogol average molecular weight measurement method described in the Japanese Pharmacopoeia. Specifically, commercially available “polyethylene glycol 400” (average molecular weight 400 ⁇ about 15) and “polyethylene glycol 600” (average molecular weight 600 ⁇ about 15) containing many fractions having a molecular weight of 400 to 600 can be used. These may be used individually by 1 type, and may mix and use 2 or more types by arbitrary ratios.
- the content of polyhydric alcohol other than polyethylene glycol is preferably 5% by mass or less, more preferably 0.5% by mass or less, and more preferably 0.05% by mass with respect to the total amount of the oxygen detector composition.
- the following is more preferable, and 0% by mass is even more preferable. That is, it is still more preferable not to contain polyhydric alcohols other than polyethylene glycol.
- the lower the content of polyhydric alcohol other than polyethylene glycol the higher the color retention at normal temperature and the color change performance of the oxygen detection agent composition.
- the redox dye of this embodiment is not limited as long as the color changes reversibly between the oxidized state and the reduced state.
- redox indicators such as ferroin and erioglaucine A; thiazine dyes such as methylene blue, new methylene blue and methylene green; azine dyes such as safranin T and phenosafranine; oxazine dyes such as Nile Blue; and indigoids such as indigo and indigo carmine Dyes; thioindigoid dyes such as thioindigo
- a thiazine dye is preferable from the viewpoint of coloring power, atmosphere responsiveness, and durability, and methylene blue is more preferable among them.
- the content of the redox dye is not particularly limited as long as the color change can be visually confirmed between the oxidized state and the reduced state.
- the content of the redox dye is 0.
- the content is preferably 01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass.
- the reducing agent used in the present embodiment is not particularly limited as long as it is a compound capable of reducing a redox dye in an oxidized state even under a condition where the oxygen concentration is lower than that in the atmosphere.
- a known reducing agent can be used as the reducing agent.
- Specific examples of the reducing agent include monosaccharides such as glucose, fructose and xylose, disaccharides such as maltose, ascorbic acid and salts thereof, dithionite and salts thereof, cysteine and salts thereof, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, monosaccharides are preferable from the viewpoint of reducing power and safety, among which fructose is more preferable, and D-fructose is more preferable.
- the content of the reducing agent is not particularly limited, but from the viewpoint of promoting the reduction reaction, it is preferably at least twice the amount of the redox dye on a substance basis.
- the molar ratio of the reducing agent to the redox dye is preferably 5 to 1000, more preferably 10 to 500, and still more preferably 50 to 300.
- the basic substance is a poorly water-soluble basic substance having a solubility in water at 20 ° C. of less than 1 g / 100 g-H 2 O, and is used for enhancing the reducing activity of the reducing agent.
- Specific examples of the poorly water-soluble basic substance include alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; calcium silicate, Silicates such as magnesium silicate and aluminum silicate; silicas, zeolites, clay minerals and the like which show basicity when made into a water slurry, are not limited thereto.
- alkaline earth metal hydroxides and alkaline earth metal carbonates are preferable, and alkaline earth metal hydroxides are more preferable from the viewpoints of price and discoloration performance.
- the basic substance may be used alone or in combination of two or more.
- the oxygen detection agent composition of this embodiment does not contain metal oxides, such as aluminum oxide, zinc oxide, and magnesium oxide.
- the oxygen detector composition of the present embodiment does not substantially contain trisodium phosphate (for example, hydrates such as trisodium phosphate dodecahydrate) as a basic substance.
- trisodium phosphate for example, hydrates such as trisodium phosphate dodecahydrate
- some attempts have been made to add a basic substance such as trisodium phosphate.
- a book that substantially does not contain trisodium phosphate has excellent responsiveness to changes in oxygen concentration and excellent color retention and printability even when stored at room temperature for a long period of time.
- substantially free of trisodium phosphate means that the content of trisodium phosphate in the oxygen detector composition is 0.8% by mass or less, and 0.5% by mass. Or less, more preferably 0.09% by mass or less, still more preferably 0.01% by mass or less, and even more preferably 0% by mass. That is, it is more preferable that the oxygen detector composition of this embodiment does not contain trisodium phosphate.
- the content of the hardly water-soluble basic substance in the oxygen detector composition is preferably 20 to 70% by mass, and more preferably 30 to 50% by mass.
- a water-soluble basic substance having a solubility in water at 20 ° C. of 1 g / 100 g-H 2 O or more is used as a basic substance as long as the effect is not impaired.
- the content of the water-soluble basic substance in the oxygen detector composition is preferably 1% by mass or less, and 0.1% by mass or less. Is more preferably 0.01% by mass or less, still more preferably 0% by mass. That is, it is even more preferable not to include a water-soluble basic substance.
- the color retention at room temperature of the oxygen detector composition can be increased as the content of the water-soluble basic substance is smaller.
- a binder can be added to the oxygen detector composition of the present embodiment.
- the binder include water-soluble polymers such as sodium alginate, gum arabic, gum tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, dextrin, polyvinyl alcohol, sodium polyacrylate, polyacrylamide; ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetyl Celluloses such as pionate; water-insoluble polymers such as vinyl acetate resin, butyral resin, polyester resin, acrylic resin, polyether resin, polyamide resin, petroleum resin; and the like.
- a solvent may be used as necessary.
- the solvent is preferably water.
- the solvent is preferably an alcohol such as methanol, ethanol or isopropyl alcohol; an ester such as ethyl acetate or butyl acetate; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; .
- a mixed solvent in which alcohols, esters, or both are mixed in an arbitrary ratio is more preferable.
- the binder content in the oxygen detector composition of the present embodiment is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and still more preferably 5 to 50% by mass.
- the oxygen detection agent composition of this embodiment contains a binder and a solvent
- the suitable viscosity differs depending on the printing technique, so the viscosity is adjusted to an appropriate viscosity according to the printing technique. It is preferable.
- the viscosity can be appropriately adjusted from the viewpoints of, for example, the strength of the coating film, thinning, and stickiness suppression.
- the viscosity of the oxygen detector composition is preferably 0.05 to 0.5 Pa ⁇ s, preferably 0.1 to 0.3 Pa ⁇ s. More preferably, it is s.
- the viscosity of the oxygen detector composition is preferably 0.01 to 0.3 Pa ⁇ s, preferably 0.05 to 0.1 Pa ⁇ s. More preferably.
- the viscosity here can be measured with a B-type viscometer.
- the color of the redox dye can be made clearer by further adding a colorant that does not change color depending on the oxygen concentration to the oxygen detector composition of the present embodiment.
- a colorant that does not change color depending on the oxygen concentration
- red No. 104, red No. 106 and the like can be mentioned, but not limited thereto.
- a food dye as a colorant.
- the content of the colorant in the oxygen detector composition is not particularly limited as long as it can be visually confirmed that the redox dye has become colorless. From the viewpoint of dispersibility and solubility of the dye in the composition, 0.01% Is preferably 5 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass.
- Additives other than those described above may be added to the oxygen detector composition of the present embodiment as necessary.
- Such additives include, for example, inorganic powders (eg, silica, zeolite, etc.) for the purpose of inhibiting stickiness of the coating film due to leaching of liquid components in the composition, and surfaces for the purpose of inhibiting blocking of the composition.
- Modifiers for example, polydimethylsiloxane, long-chain alkanes, inorganic powders with a hydrophobic surface
- thickeners for the purpose of preventing and homogenizing the aggregation and sedimentation of particles in the composition by adjusting the viscosity Etc.
- an oxygen detection agent composition is not specifically limited, It can also manufacture by mixing the substance mentioned above by a well-known method.
- an oxygen detector composition comprising a mixture of the above-mentioned redox dye, reducing agent, polyethylene glycol, basic substance and solvent is impregnated into a fibrous base material such as paper, yarn, nonwoven fabric, etc., and dried to form a filamentous shape.
- a sheet-like (sometimes referred to as “film-like”) oxygen detector is referred to as “film-like”.
- the oxygen detector composition of this embodiment can be used as an oxygen detector sheet, a packaging material for oxygen absorber, an oxygen absorber package, and the like.
- Examples of the oxygen detection sheet include an oxygen detection sheet containing the oxygen detection agent composition of the present embodiment.
- an oxygen detection sheet for example, a solution in which a binder is dissolved in a mixed solvent of alcohols and esters is prepared, and polyethylene glycol, a redox dye, and a reducing agent are added thereto, and then dispersed and mixed in the form of an ink.
- An oxygen detection sheet can be manufactured by preparing an oxygen detection agent composition, applying or impregnating the substrate, and then drying.
- the oxygen detector composition can be directly applied or printed on the substrate, it may be effective to apply a seal between them for the purpose of improving the adhesion of the composition to the substrate. is there.
- a varnish of a flexible resin such as polyurethane resin or natural rubber can be used.
- an over primer to a coating layer of the oxygen detector composition (hereinafter sometimes referred to as “oxygen detector layer”, “layer containing the oxygen detector composition”, etc.). May be useful for layer protection.
- the over primer the same primer as the above-mentioned seal can be used.
- the base material examples include plastic base materials such as polyester, polyolefin, and polyvinyl chloride, and fibrous base materials such as paper and non-woven fabric.
- a technique such as applying, impregnating, or printing the oxygen detector composition to the substrate can be employed.
- the method for applying the oxygen detector composition to the substrate include a method using a spray or a bar coater.
- the method for printing the oxygen detector composition on the substrate include an offset printing method, a gravure printing method, a screen printing method, a flexographic printing method, and a relief printing method.
- the substrate may be a single layer or a plurality of layers.
- the oxygen detector layer in order to make the color of the coating part visible, at least one of the upper layer and the lower layer of the coating layer is substantially transparent. It is necessary to.
- the drying temperature at the time of applying the above-described liquid oxygen detector composition to the substrate is not particularly limited as long as the solvent or the like can be volatilized, but from the viewpoint of preventing the oxygen detector composition from being discolored by heat. It is preferably not higher than ° C., more preferably not higher than 80 ° C., and further preferably not higher than 70 ° C.
- the oxygen scavenger packaging material including the oxygen detection sheet described above can be used.
- the oxygen detection sheet has a plurality of layers such as an outer surface layer / an oxygen detection agent layer (a layer containing an oxygen detection agent composition) / an inner surface layer. That is, it has at least an outer surface layer, an oxygen detector layer provided on the outer surface layer, and an inner surface layer provided on the oxygen detector layer, and the oxygen detector layer detects oxygen.
- the structure etc. which are the layers containing an agent composition are preferable.
- the inner surface layer is a layer in contact with the oxygen scavenger composition.
- the outer surface layer is a layer in contact with the outside, and is a surface layer located on the side opposite to the oxygen scavenger composition stored inside. Therefore, when the oxygen scavenger composition is packaged with the oxygen scavenger packaging material, for example, the outer surface layer / oxygen detector layer / inner surface layer / oxygen scavenger composition can be contacted in this order.
- the inner surface layer is preferably a layer having heat sealability (heat seal layer) for directly packaging the oxygen scavenger composition.
- a layer including a low density polyethylene film is preferable.
- the outer surface layer is a layer in contact with the outside, the outer surface layer is preferably a layer containing polyethylene terephthalate or the like.
- the oxygen detector composition it is preferable to further have a layer containing a transparent resin as a protective layer on the oxygen detector layer.
- the protective layer only needs to be able to visually recognize the discoloration of the oxygen detecting agent layer from the outside, and may be provided between the outer surface layer and the oxygen detecting agent layer or between the inner surface layer and the oxygen detecting agent layer. May be.
- As a method of providing a protective layer on the oxygen detector layer it is preferable to provide a portion (layer) containing the oxygen detector composition by back printing of a film.
- a laminating method after printing dry laminating is preferable from the viewpoint that the oxygen detecting agent portion is not easily exposed to high temperatures.
- Examples of the oxygen scavenger package of the present embodiment include an oxygen scavenger package including the oxygen scavenger composition and the oxygen scavenger package that packages the oxygen scavenger composition.
- the oxygen scavenger composition is not particularly limited as long as it can absorb oxygen and form a deoxygenated state (for example, an oxygen concentration of 0.1% or less).
- the method of packaging the oxygen scavenger composition with the oxygen scavenger package is not particularly limited, and is known, for example, three-way packaging using a rotary packer, pillow packaging using a stick packer, four-way packaging using a four-way packaging machine, etc. Packaging machines and packaging methods can be used. Among these, three-way packaging with a rotary packer or the like is preferable from the viewpoint of production efficiency.
- IPA isopropyl alcohol
- ethyl acetate ethyl acetate
- methylene blue methylene green
- D-fructose D-xylose
- magnesium hydroxide magnesium carbonate
- trisodium phosphate twelve water ethyl alcohol
- reagents manufactured by Wako Pure Chemical Industries, Ltd. were used for Japanese products, glycerin, polyethylene glycol 200 (hereinafter referred to as “PEG200”) and all the water retention agents shown in Table 1.
- Example 1 ⁇ Production of oxygen indicator ink> A mixed solvent of 4.5 g of IPA and 4.5 g of ethyl acetate is prepared, and cellulose acetate propionate (trade name “504-0.2”, manufactured by EASTMAN CHEMICAL, hereinafter referred to as “CAP”) is used as a binder. 0 g was dissolved. In this solution, 0.016 g of methylene blue as a redox dye, 0.011 g of Phloxine B (edible red No.
- CAP cellulose acetate propionate
- Ink A was obtained by adding and dispersing 2.1 g of D-fructose as a reducing agent.
- the content of PEG 200 was 25% by mass with respect to the total amount of the composition.
- Ink B was obtained by mixing and dispersing 10 g of magnesium hydroxide (solubility in water at 20 ° C .: 0.9 mg / 100 g-H 2 O) as a hardly water-soluble basic substance in this solution.
- Oxygen indicator ink was obtained by mixing 1.1 g of ink A, 1.1 g of ink B, 0.7 g of IPA and 0.7 g of ethyl acetate.
- Ink was applied to the surface of YUPO paper (FPD-80, manufactured by YUPO CORPORATION) cut to 100 mm ⁇ 150 mm by the following procedure.
- the ink was applied using a bar coater (manufactured by Tester Sangyo Co., Ltd.).
- “CLIOS medium (A)” manufactured by DIC Graphics Co., Ltd.
- the oxygen indicator ink obtained as an oxygen detection layer was applied and dried with hot air at 60 ° C. for 10 seconds.
- “CLIOS medium” (A) manufactured by DIC Graphics Co., Ltd.
- the obtained oxygen detection sheet was cut into a size of 5 mm ⁇ 15 mm and fixed with tape in the oxygen barrier bag.
- the bag is sealed with moisture-controlling cotton and an oxygen scavenger ("Ageless SA-100" manufactured by Mitsubishi Gas Chemical Co., Inc .; self-reactive iron-based oxygen scavenger) and nitrogen 500mL. Sealed.
- an oxygen scavenger (Ageless SA-100” manufactured by Mitsubishi Gas Chemical Co., Inc .; self-reactive iron-based oxygen scavenger) and nitrogen 500mL. Sealed.
- the bag was stored at 25 ° C., The color tone of the oxygen detection sheet was visually confirmed every 6 hours.
- the obtained oxygen detection sheet was cut into a size of 5 mm ⁇ 15 mm and fixed with tape in the oxygen barrier bag.
- an oxygen scavenger (“AGELESS SA-202”, a self-reactive iron-based oxygen scavenger) manufactured by Mitsubishi Gas Chemical Co., Inc., a moisture-controlling cotton that adjusts the humidity to 70% RH, and 250 mL of air are enclosed in the bag. And sealed. After the sealed bag was stored at 35 ° C. for one month, the color of the oxygen detection sheet in the sealed bag was visually confirmed.
- oxygen detection sheet A oxygen detection sheet
- oxygen detection sheet B another oxygen detection sheet
- the state of ink adhesion on the surface of the oxygen detection sheet B on which no ink was applied was visually observed.
- the case without ink adhesion was evaluated as “A”
- the case with ink adhesion was evaluated as “C”. The results are shown in Table 1.
- Examples 2 to 6, Comparative Examples 1 to 8 An oxygen detector and an oxygen detection sheet were produced in the same manner as in Example 1 except that the substance shown in Table 1 was used as the water retention agent instead of PEG200. Then, in the same manner as in Example 1, the color change performance evaluation, the color retention evaluation, and the printability evaluation were performed. The results are shown in Table 1. In addition, about the average molecular weight of Table 1, polyethyleneglycol was calculated
- Polyethylene glycol 200 (average molecular weight: 190-210) “Polyethylene glycol 300” (average molecular weight: 280 to 320) “Polyethylene glycol 400” (average molecular weight: 380 to 420) “Polyethylene glycol 600” (average molecular weight: 570 to 630) “Polyethylene glycol 1000” (average molecular weight: 900-1100) "Polyethylene glycol 1540" (average molecular weight: 1500)
- those used in addition to polyethylene glycol are shown below.
- Ethylene glycol (Made in Wako Pure Chemical Industries, molecular weight 62) Propylene glycol (Wako Pure Chemical Industries, Ltd., molecular weight 76) Dipropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 134) Propylene glycol monomethyl ether (Wako Pure Chemical Industries, Ltd., molecular weight 90) Diethylene glycol (Wako Pure Chemical Industries, Ltd., molecular weight 106) Polypropylene glycol 300 (manufactured by Wako Pure Chemical Industries, Ltd., product molecular weight 300) Polypropylene glycol 700 (manufactured by Wako Pure Chemical Industries, Ltd., product molecular weight 700) Polypropylene glycol 2000 (manufactured by Wako Pure Chemical Industries, Ltd., product molecular weight 2000)
- Redox dye methylene blue reducing agent: D-fructose poorly soluble basic substance: magnesium hydroxide water retention agent content: 25% by mass
- Examples 7 to 12, Comparative Examples 9 to 10 An oxygen detector and an oxygen detection sheet were produced in the same manner as in Example 1 except that the blending amount of PEG 200 was changed to the content (% by mass) shown in Table 2. That is, “PEG content” shown in Table 2 represents the content (% by mass) of PEG 200 with respect to the total amount of the oxygen detector composition after drying. And about these, it carried out similarly to Example 1, and performed performance evaluation. The results are shown in Table 2.
- Example 13 Comparative Example 11
- An oxygen detector and an oxygen detection sheet were prepared in the same manner as in Example 1 except that methylene green was used as the redox dye instead of methylene blue (Example 13). Further, an oxygen detector and an oxygen detection sheet were produced in the same manner as in Comparative Example 1 except that methylene green was used as the redox dye instead of methylene blue (Comparative Example 11). About Example 13 and Comparative Example 11, each performance evaluation was performed. In Example 13, the color change performance, the color retention, and the printability were all “A”, but in Comparative Example 11, the color retention was “C”.
- Example 14 Comparative Example 12
- An oxygen detector and an oxygen detection sheet were prepared in the same manner as in Example 1 except that D-xylose was used as a reducing agent instead of D-fructose (Example 14). Further, an oxygen detection agent and an oxygen detection sheet were prepared in the same manner as in Comparative Example 1 except that D-xylose was used as a reducing agent instead of D-fructose (Comparative Example 12). Performance evaluation was performed on Example 14 and Comparative Example 12, respectively. In Example 14, the color change performance, the color retention and the printability were all “A”, but in Comparative Example 12, the color retention was “C”.
- Example 15 Comparative Example 13
- magnesium carbonate solubility in water at 20 ° C .: 0.039 g / 100 g-H 2 O
- An oxygen detection agent and an oxygen detection sheet were prepared (Example 15).
- Each of Example 15 and Comparative Example 13 was evaluated for performance. In Example 15, the color change performance, color retention, and printability were all “A”, but in Comparative Example 13, color retention was “C”.
- Table 3 shows the results of Examples 13 to 15 and Comparative Examples 11 to 14.
- the oxygen detector composition, oxygen detection sheet, oxygen absorber packaging material, and oxygen absorber package according to the present invention can be stored and distributed for a long time at room temperature. Therefore, it is not necessary to store at low temperature, and it is easy to manage and has a large energy saving effect, so it can be used for food and medicine storage, metal and rubber product storage, atmosphere control and management, microbial culture, cell culture, etc. It has applicability in a wide range of fields including the beginning.
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Abstract
Description
<1>
ポリエチレングリコール、酸化還元色素、還元剤及び塩基性物質を含む酸素検知剤組成物であって、
前記ポリエチレングリコールの含有量が、前記酸素検知剤組成物の総量に対して5~35質量%であり、
前記塩基性物質が、20℃での水への溶解度が1g/100g-H2O未満の水難溶性塩基性物質であり、
リン酸三ナトリウムを実質的に含まない、酸素検知剤組成物。
<2>
前記ポリエチレングリコールの平均分子量が、200~700である、<1>に記載の酸素検知剤組成物。
<3>
前記塩基性物質が、アルカリ土類金属水酸化物、アルカリ土類金属炭酸塩、又はその両方である、<1>又は<2>に記載の酸素検知剤組成物。
<4>
前記酸素検知剤組成物における、20℃での水への溶解度が1g/100g-H2O以上である水溶性塩基性物質の含有量が、1質量%以下である、<1>~<3>の何れか一項に記載の酸素検知剤組成物。
<5>
<1>~<4>の何れか一項に記載の酸素検知剤組成物を含む酸素検知シート。
<6>
<5>に記載の酸素検知シートを含む脱酸素剤用包装材料。
<7>
脱酸素剤組成物と、
前記脱酸素剤組成物を包装する、<6>に記載の脱酸素剤用包装材料と、
を含む、脱酸素剤包装体。
本実施形態の酸素検知剤組成物は、保水剤としてポリエチレングリコールを用いる。酸素検知剤組成物におけるポリエチレングリコールの含有量は、5~35質量%である。ポリエチレングリコールの含有量は、10~30質量%であることが好ましく、12~20質量%であることがより好ましい。ポリエチレングリコールの含有量を上記範囲内とすることで、後述する酸化還元色素の酸化還元反応が促進されて、酸素濃度変化に対する応答性が良好となり、常温で長期間保存した後も酸素検知剤組成物の色彩変化を抑制することができると共に、酸素検知剤組成物のべたつきが抑制され、良好な印刷適性が得られる。
本実施形態の酸化還元色素は、酸化状態と還元状態で可逆的に色が変化するものであれば、何ら限定されない。例えば、フェロイン、エリオグラウシンA等の酸化還元指示薬;メチレンブルー、ニューメチレンブルー、メチレングリーン等のチアジン染料;サフラニンT、フェノサフラニン等のアジン染料;ナイルブルー等のオキサジン染料;インジゴ、インジゴカルミン等のインジゴイド染料;チオインジゴ等のチオインジゴイド染料等が挙げられる。これらの中でも、着色力、雰囲気応答性及び耐久性の観点から、チアジン染料が好ましく、その中でもメチレンブルーがより好ましい。
本実施形態で用いられる還元剤は、酸素濃度が大気中より低い条件であっても、酸化状態にある酸化還元色素を還元できる化合物であればよく、その種類は特に限定されない。還元剤としては、公知の還元剤を用いることもできる。還元剤の具体例としては、例えば、グルコース、フルクトース、キシロース等の単糖類、マルトース等の二糖類、アスコルビン酸及びその塩、亜ジチオン酸及びその塩、システイン及びその塩等挙げられる。これらは、1種単独で用いてもよいし、2種以上を併用してもよい。これらの中でも、還元力及び安全性の観点から単糖類が好ましく、その中でもフルクトースがより好ましく、D-フルクトースが更に好ましい。
塩基性物質は、20℃での水への溶解度が1g/100g-H2O未満の水難溶性塩基性物質であり、還元剤の還元活性等を高めるために用いられる。水難溶性塩基性物質としては、具体的には、水酸化カルシウム、水酸化マグネシウム等のアルカリ土類金属の水酸化物;炭酸マグネシウム、炭酸カルシウム等のアルカリ土類金属の炭酸塩;ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸アルミニウム等のケイ酸塩;シリカ、ゼオライト、粘土鉱物等のうち水スラリーとした際に塩基性を示すもの等が挙げられるが、これらに限定されない。これらの中でも、価格や変色性能の観点から、アルカリ土類金属水酸化物、アルカリ土類金属炭酸塩が好ましく、アルカリ土類金属水酸化物がより好ましい。本実施形態の効果が得られる範囲であれば、塩基性物質は、1種単独で用いてもよいし、2種以上を併用してもよい。そして、本実施形態の酸素検知剤組成物は、酸化アルミニウム、酸化亜鉛、酸化マグネシウム等の金属酸化物を含まないことが好ましい。
本実施形態の酸素検知剤組成物には、必要に応じてバインダーを添加することができる。バインダーとしては、例えば、アルギン酸ナトリウム、アラビアゴム、トラガントガム、カルボキシメチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、デキストリン、ポリビニルアルコール、ポリアクリル酸ナトリウム、ポリアクリルアミド等の水溶性高分子;エチルセルロース、エチルヒドロキシエチルセルロース、セルロースアセチルプロピオネート等のセルロース類;酢酸ビニル樹脂、ブチラール樹脂、ポリエステル樹脂、アクリル樹脂、ポリエーテル樹脂、ポリアミド樹脂、石油系樹脂等の水不溶性高分子;等が挙げられる。
本実施形態の酸素検知剤組成物には、酸素濃度によって変色しない着色剤を更に加えることで、酸化還元色素の変色をより鮮明にすることができる。例えば、赤色104号、赤色106号等が挙げられるが、これらに限定されない。例えば、食品や医薬を保存する容器中の酸素検知を行う場合には、着色剤として食用染料を用いることが好ましい。酸素検知剤組成物における着色剤の含有量は、酸化還元色素が無色になったことが目視で確認できれば特に限定されないが、組成物への色素の分散性や溶解性の観点から、0.01~5質量%であることが好ましく、0.05~3質量%であることがより好ましく、0.1~1質量%であることが更に好ましい。
本実施形態の酸素検知剤組成物には、必要に応じて、上記以外の他の添加剤を添加することもできる。このような添加剤としては、例えば、組成物中の液体成分の染み出しによる塗膜べたつき抑制を目的とする無機粉体(例えば、シリカ、ゼオライト等)、組成物のブロッキング抑制を目的とする表面改質剤(例えば、ポリジメチルシロキサン、長鎖アルカン、表面を疎水化処理した無機粉体等)、粘度調整による組成物中の粒子の凝集や沈降の防止及び均質化を目的とする増粘剤等が挙げられる。
酸素検知剤組成物の製造方法は、特に限定されず、上述した物質を公知の方法で混合することで製造することもできる。例えば、上記の酸化還元色素、還元剤、ポリエチレングリコール、塩基性物質及び溶剤を混合してなる酸素検知剤組成物は、紙、糸、不織布等の繊維質基材へ含浸後乾燥させることで糸状やシート状(「フィルム状」と呼ばれることもある。)の酸素検知体を得ることができる。
本実施形態の酸素検知剤組成物は、酸素検知シート、脱酸素剤用包装材料、脱酸素剤包装体等として用いることができる。
<酸素インジケーターインキの作製>
IPA4.5g及び酢酸エチル4.5gの混合溶媒を用意し、バインダーとしてセルロースアセテートプロピオネート(商品名「504-0.2」、EASTMAN CHEMICAL社製、以下「CAP」と表記する。)1.0gを溶解させた。この溶液に、酸化還元色素としてメチレンブルー0.016g、着色剤としてフロキシンB(食用赤色104号、保土谷化学株式会社製)0.011g、保水剤としてPEG200を3.6g(乾燥後の酸素検知剤組成物の総量に対するPEG200の含有率は25質量%)、還元剤としてD-フルクトース2.1gを加えて分散させることによりインキAを得た。
100mm×150mmに切り取ったユポ紙(FPD-80、株式会社ユポコーポレーション製)の表面に以下の手順によりインキを塗布した。インキの塗布はバーコーター(テスター産業株式会社製)を用いて行った。まず、保護層として「CLIOSメジウム (A)」(DICグラフィックス株式会社製)を塗布し、60℃の温風により10秒間乾燥させた。次いで、酸素検知層として得られた酸素インジケーターインキを塗布し、60℃の温風により10秒間乾燥させた。最後に、もう一度「CLIOSメジウム」(A)(DICグラフィックス株式会社製)を、塗布し、60℃の温風により10秒間乾燥させることにより酸素検知シートを得た。
得られた酸素検知シートを5mm×15mmの大きさに切り出し、酸素バリア袋内にテープで固定した。次いで、該袋に80%RHに調湿する調湿綿と脱酸素剤(三菱瓦斯化学株式会社製、「エージレスSA-100」;自力反応型の鉄系脱酸素剤)及び窒素500mLを封入し密封した。袋内の酸素濃度が0.1容量%未満となっていることを、ガスクロマトグラフィー(株式会社島津製作所製、「GC-14A」)を用いて確認した後に該袋を25℃で保存し、酸素検知シートの色調を6時間ごとに目視で確認した。酸素濃度が0.1容量%未満になっていることを示すピンク色に変色するまでに要した時間が6時間以内であった場合を「A」、12時間以内であった場合を「B」、18時間以上であった場合を「C」と評価した。なお、80%RHに調湿する調湿綿は、グリセリン2.55g及び水2.45gを混合し脱脂綿に含浸させることにより作製した。
得られた酸素検知シートを5mm×15mmの大きさに切り出し、酸素バリア袋内にテープで固定した。次いで、該袋に脱酸素剤(三菱瓦斯化学株式会社製、「エージレスSA-202」、自力反応型の鉄系脱酸素剤)、70%RHに調湿する調湿綿及び空気250mLを封入して密封した。該密封袋を35℃で1ヵ月保存した後に、該密封袋内の酸素検知シートの色彩を目視で確認した。保存前後で色彩に変化が無かった場合を「A」、色彩が変化しているが酸素濃度視認できた場合を「B」、色彩が変化し酸素濃度視認が困難であった場合を「C」と評価した。結果を表1に示す。なお、70%RHに調湿する調湿綿は、グリセリン3.15g及び水1.85gを混合し、脱脂綿に含浸させることにより作製した。
得られた酸素検知シートを2枚用意し、1枚の酸素検知シート(以下、「酸素検知シートA」と表記する。)をインキ塗布面が上向きとなるよう置いた。次に、もう1枚の酸素検知シート(以下、「酸素検知シートB」と表記する。)をインキ塗布面が上向きとなるよう酸素検知シートAの上に重ねて置いた。その後、酸素検知シートBのインキを塗布していない面(酸素検知シートAのインキ塗布面と接触した面)のインキ付着の状態を、目視で観察した。インキ付着が無かったものを「A」、インキ付着があったものを「C」と評価した。結果を表1に示す。
PEG200に代えて、保水剤として表1に示した物質を用いた点以外は、実施例1と同様にして、酸素検知剤と酸素検知シートを作製した。そして、これらについて、実施例1と同様にして、変色性能評価、色彩保持性評価及び印刷適性評価を行った。その結果を表1に示す。なお、表1に記載の平均分子量に関して、ポリエチレングリコールは日本薬局方記載のマクロゴールの平均分子量測定法によって求めた。
使用したポリエチレングリコールを以下に示す。
「ポリエチレングリコール200」(平均分子量:190~210)
「ポリエチレングリコール300」(平均分子量:280~320)
「ポリエチレングリコール400」(平均分子量:380~420)
「ポリエチレングリコール600」(平均分子量:570~630)
「ポリエチレングリコール1000」(平均分子量:900~1100)
「ポリエチレングリコール1540」(平均分子量:1500)
なお、ポリエチレングリコール以外に使用したものを以下に示す。
エチレングリコール(和光純薬工業株式会社製、分子量62)
プロピレングリコール(和光純薬工業株式会社製、分子量76)
ジプロピレングリコール(和光純薬工業株式会社製、分子量134)
プロピレングリコールモノメチルエーテル(和光純薬工業株式会社製、分子量90)
ジエチレングリコール(和光純薬工業株式会社製、分子量106)
ポリプロピレングリコール300(和光純薬工業株式会社製、商品記載の分子量300)
ポリプロピレングリコール700(和光純薬工業株式会社製、商品記載の分子量700)
ポリプロピレングリコール2000(和光純薬工業株式会社製、商品記載の分子量2000)
PEG200の配合量を表2に示した含有率(質量%)に変更した点以外は、実施例1と同様にして、酸素検知剤と酸素検知シートを作製した。すなわち、表2に記載の「PEG含有率」は、乾燥後の酸素検知剤組成物の総量に対するPEG200の含有率(質量%)を示す。そして、これらについて、実施例1と同様にして、性能評価を行った。その結果を表2に示す。
メチレンブルーに代えて、酸化還元色素としてメチレングリーンを用いた点以外は、実施例1と同様にして、酸素検知剤と酸素検知シートを作製した(実施例13)。また、メチレンブルーに代えて、酸化還元色素としてメチレングリーンを用いた点以外は、比較例1と同様にして、酸素検知剤と酸素検知シートを作製した(比較例11)。実施例13及び比較例11について、各々性能評価を行った。実施例13では変色性能、色彩保持性及び印刷適性が全て「A」であったが、比較例11では色彩保持性が「C」であった。
D-フルクトースに代えて、還元剤としてD-キシロースを用いた点以外は、実施例1と同様にして、酸素検知剤と酸素検知シートを作製した(実施例14)。また、D-フルクトースに代えて、還元剤としてD-キシロースを用いた点以外は、比較例1と同様にして、酸素検知剤と酸素検知シートを作製した(比較例12)。実施例14及び比較例12について、各々性能評価を行った。実施例14では変色性能、色彩保持性及び印刷適性が全て「A」であったが、比較例12では色彩保持性が「C」であった。
水酸化マグネシウムに代えて、水難溶性塩基性物質として炭酸マグネシウム(20℃での水への溶解度:0.039g/100g-H2O)を用いた点以外は、実施例1と同様にして、酸素検知剤と酸素検知シートを作製した(実施例15)。また、水酸化マグネシウムに代えて、水難溶性塩基性物質として炭酸マグネシウムを用いた点以外は、比較例1と同様にして、酸素検知剤と酸素検知シートを作製した(比較例13)。実施例15及び比較例13について、各々性能評価を行った。実施例15では変色性能、色彩保持性及び印刷適性が全て「A」であったが、比較例13では色彩保持性が「C」であった。
インキBに対してリン酸三ナトリウム十二水和物(20℃での水への溶解度:12.1g/100g-H2O(無水物換算))0.4g(乾燥後の酸素検知剤組成物の総量に対するリン酸三ナトリウム十二水和物の含有量は2質量%であり、リン酸三ナトリウムの無水物換算の含有量は0.86質量%)を更に添加して混合分散した点以外は、実施例1と同様にして、酸素検知剤と酸素検知シートを作製し、性能評価を行った。比較例14では色彩保持性が「C」であった。
Claims (7)
- ポリエチレングリコール、酸化還元色素、還元剤及び塩基性物質を含む酸素検知剤組成物であって、
前記ポリエチレングリコールの含有量が、前記酸素検知剤組成物の総量に対して5~35質量%であり、
前記塩基性物質が、20℃での水への溶解度が1g/100g-H2O未満の水難溶性塩基性物質であり、
リン酸三ナトリウムを実質的に含まない、酸素検知剤組成物。 - 前記ポリエチレングリコールの平均分子量が、200~700である、請求項1に記載の酸素検知剤組成物。
- 前記塩基性物質が、アルカリ土類金属水酸化物、アルカリ土類金属炭酸塩、又はその両方である、請求項1又は2に記載の酸素検知剤組成物。
- 前記酸素検知剤組成物における、20℃での水への溶解度が1g/100g-H2O以上である水溶性塩基性物質の含有量が、1質量%以下である、請求項1~3の何れか一項に記載の酸素検知剤組成物。
- 請求項1~4の何れか一項に記載の酸素検知剤組成物を含む酸素検知シート。
- 請求項5に記載の酸素検知シートを含む脱酸素剤用包装材料。
- 脱酸素剤組成物と、
前記脱酸素剤組成物を包装する、請求項6に記載の脱酸素剤用包装材料と、
を含む、脱酸素剤包装体。
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WO2017141418A1 (ja) * | 2016-02-19 | 2017-08-24 | 株式会社常盤産業 | 酸素検知用組成物および酸素検知体 |
WO2021215288A1 (ja) * | 2020-04-22 | 2021-10-28 | 三菱瓦斯化学株式会社 | 炭酸ガス検知体 |
Families Citing this family (4)
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EP3509054B1 (en) * | 2016-08-31 | 2024-07-03 | Tokiwa Sangyo Co., Ltd. | Display medium |
RU2656132C2 (ru) * | 2016-11-22 | 2018-05-31 | Общество С Ограниченной Ответственностью "Газпром Трансгаз Краснодар" | Способ определения концентрации диэтиленгликоля в стабильных жидких углеводородных фракциях |
TWI623470B (zh) * | 2017-02-03 | 2018-05-11 | Zhang Shi Jie | Deoxidizer |
KR102539206B1 (ko) * | 2021-02-02 | 2023-05-31 | 경상국립대학교산학협력단 | 시각화 잉크 조성물 |
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- 2014-07-16 CN CN201480040461.XA patent/CN105378472A/zh active Pending
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- 2014-07-16 EP EP14826219.9A patent/EP3023783A4/en not_active Withdrawn
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017141418A1 (ja) * | 2016-02-19 | 2017-08-24 | 株式会社常盤産業 | 酸素検知用組成物および酸素検知体 |
CN108603869A (zh) * | 2016-02-19 | 2018-09-28 | 株式会社常盘产业 | 氧检测用组合物和氧检测体 |
JPWO2017141418A1 (ja) * | 2016-02-19 | 2019-01-10 | 株式会社常盤産業 | 酸素検知用組成物および酸素検知体 |
EP3428638A4 (en) * | 2016-02-19 | 2019-11-06 | Tokiwa Sangyo Co., Ltd. | OXYGEN DETECTION COMPOSITION, AND OXYGEN DETECTOR |
US10802007B2 (en) | 2016-02-19 | 2020-10-13 | Tokiwa Sangyo Co., Ltd. | Oxygen detecting composition and oxygen detecting body |
WO2021215288A1 (ja) * | 2020-04-22 | 2021-10-28 | 三菱瓦斯化学株式会社 | 炭酸ガス検知体 |
Also Published As
Publication number | Publication date |
---|---|
US20160153946A1 (en) | 2016-06-02 |
EP3023783A1 (en) | 2016-05-25 |
JPWO2015008792A1 (ja) | 2017-03-02 |
EP3023783A4 (en) | 2017-03-29 |
KR20160031486A (ko) | 2016-03-22 |
CN105378472A (zh) | 2016-03-02 |
JP6459966B2 (ja) | 2019-01-30 |
TW201510507A (zh) | 2015-03-16 |
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