Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
  • A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
  • A23B2/729—Organic compounds; Microorganisms; Enzymes
  • A23B2/742—Organic compounds containing oxygen
  • A23B2/754—Organic compounds containing oxygen containing carboxyl groups
  • A23B2/758—Carboxylic acid esters
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
  • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
  • A23B7/153—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
  • A23B7/154—Organic compounds; Microorganisms; Enzymes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to a coating composition, fruits and vegetables coated with the composition, and a method for preserving the freshness of fruits and vegetables.
• packaging materials capable of maintaining the freshness of food during distribution or storage such as modified atmosphere (MA) packaging
• MA modified atmosphere
• a technology has been proposed for preserving the freshness of food by providing a layer having a freshness-preserving effect on a film for packaging food (see Patent Document 1).
• a technique has been proposed in which a quality preserving agent is directly applied to food such as fruits and vegetables to preserve the freshness of the food (see Patent Documents 2 and 3).
• Patent Documents 4 and 5 disclose compositions containing glycerol fatty acid esters as compositions that can be used to form protective coatings on substrates, and are said to be usable to protect substrates, such as food and/or agricultural products, from deterioration and/or decomposition due to factors such as moisture loss, oxidation, mechanical decomposition, photodecomposition, and mold growth.
• Patent Document 1 since food may come into contact with the packaging film during distribution or storage, it is preferable that the layer having a freshness-preserving effect is also highly safe for the human body. Furthermore, the methods disclosed in the above-mentioned Patent Documents 2 and 3 only have a short freshness retention period and are not necessarily sufficient in terms of achieving freshness retention performance. Furthermore, although the compositions disclosed in Patent Documents 4 and 5 have a freshness-preserving effect, they have problems in that they are not necessarily easy to apply and are difficult to handle. Patent Document 6 describes an agent for preventing damage to fruit and vegetables from peel damage, which contains a surfactant with an HLB of 5 or less as an active ingredient.
• Patent Document 6 The purpose of this is to prevent water from entering through the fruit and vegetables peel, and to effectively prevent damage to the fruit peel while preventing the adverse effects of coating with oils and fats.
• a surfactant alone is difficult to disperse and dissolve in water, but this difficulty is overcome by using an emulsifier.
• the method for producing the agent for preventing damage to the fruit peel is to add a surfactant that has been heated and melted to an emulsifier that has been heated and dissolved in a heated state. Although the method of Patent Document 6 prevents damage to the fruit peel to a certain extent, it is believed that further improvement can be made in terms of maintaining freshness.
• the objective of the present invention is to propose a coating composition that can directly form a film with freshness-preserving properties without using a packaging material, coated fruits and vegetables using said composition, and a method for preserving the freshness of fruits and vegetables.
• a coating composition containing a sugar-based surfactant and a glycerin fatty acid ester wherein the mass ratio (solid content) of the sugar-based surfactant to the total mass of the sugar-based surfactant and the glycerin fatty acid ester is 1% or more and less than 100%, and the glycerin fatty acid ester having three fatty acid ester groups accounts for 50% or less by mass.
• the coating composition according to the above [1] having a shear viscosity at a shear rate of 1 s -1 of 0.1 to 8000 mPa ⁇ s.
• the aqueous solvent comprises water or a mixed solvent of a water-soluble organic solvent and water.
• the non-volatile component concentration is 0.1% by mass or more and 60% by mass or less.
• a method for preserving the freshness of fruits and vegetables comprising a step of covering fruits and vegetables with the coating composition according to any one of [1] to [7] above.
• the method for preserving the freshness of fruits and vegetables described in [10] above, wherein the step of covering the fruits and vegetables with the coating composition is a step of immersing the fruits and vegetables in the composition or applying or spraying the composition onto the fruits and vegetables.
• the present invention provides a coating composition that can directly form a coating with freshness-preserving properties without using a packaging material, coated fruits and vegetables using the composition, and a method for preserving the freshness of fruits and vegetables.
• the coating composition of the present invention (hereinafter sometimes referred to as "the composition") contains a sugar-based surfactant and a glycerin fatty acid ester, the mass ratio (solid content) of the sugar-based surfactant to the total mass of the sugar-based surfactant and the glycerin fatty acid ester is 1% or more and less than 100%, and the glycerin fatty acid ester (triester) having three fatty acid ester groups is 50% or less by mass.
• the coating composition of the present invention can be suitably used for fruits and vegetables.
• Sugar-based surfactants are surfactants that have sugars, such as monosaccharides, disaccharides, trisaccharides, tetrasaccharides, polysaccharides, sugar alcohols, and other oligosaccharides, as the hydrophilic group.
• sugar-based surfactants include sugar fatty acid esters formed by ester bonds between sugars and fatty acids, and alkyl glycosides formed by glycosidic bonds between sugars and higher alcohols. Of these, sugar fatty acid esters are preferred from the standpoint of film-forming properties.
• the sugar-based surfactant is preferably crystalline from the viewpoints of suppressing stickiness of the resulting coating and improving the water vapor barrier property and oxygen barrier property.
• the sugar-based surfactant preferably contains 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more of a component that is solid at room temperature (20 to 25° C.).
• the sugar-based surfactant may be composed only of a component that is solid at room temperature (20 to 25° C.), and therefore the above ratio may be 100% by mass or less.
• the HLB of the sugar-based surfactant is not particularly limited, but from the viewpoint of being able to form a coating using an aqueous solvent described below, it is preferably 5 or more, more preferably 7 or more, and even more preferably 9 or more.
• the upper limit of the HLB is usually 20, and more preferably 18 or less.
• the sugar-based surfactant of the present invention may comprise a sugar fatty acid ester.
• Sugar fatty acid esters are formed by esterifying sugar and fatty acids.
• the sugar in the sugar fatty acid ester may be any one of monosaccharides, disaccharides, trisaccharides, tetrasaccharides, polysaccharides, sugar alcohols and other oligosaccharides.
• monosaccharides include pentoses such as ribulose, xylulose, ribose, arabinose, xylose, lyxose, and deoxyribose; and hexoses such as psicose, fructose, sorbose, tagatose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose, fuculose, and rhamnose.
• the fatty acids constituting the sugar fatty acid ester may be the same as the fatty acids constituting the sucrose fatty acid ester described below.
• the constituent fatty acids of the sugar fatty acid ester do not need to be all the same, and it is sufficient that 60% by mass or more of the constituent fatty acids in the sugar fatty acid ester are suitable constituent fatty acids described below. From the viewpoint of suppressing the stickiness of the resulting coating, this ratio is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. There is no particular limit to the upper limit, but it is sufficient that it is 100% by mass or less.
• the fatty acid composition of the sugar fatty acid ester can be measured by isolating the sugar fatty acid ester from the composition, derivatizing it, and then analyzing it by gas chromatography.
• the number of fatty acid ester groups in a sugar fatty acid ester varies depending on the number of hydroxyl groups capable of forming an ester bond in the molecular structure of the sugar, which is a hydrophilic group; for example, 1 to 8 for sucrose fatty acid esters and 1 to 4 for sorbitan fatty acid esters.
• the sugar-based surfactant contains 50% by mass or more of sugar fatty acid esters (monoesters, diesters, or triesters) having 3 or less fatty acid ester groups, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
• sugar fatty acid esters monoesters, diesters, or triesters
• the sugar fatty acid ester having 6 or more fatty acid ester groups (hexaester, heptaester, octaester or more) is preferably contained in an amount of 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the sugar fatty acid ester having 6 or more fatty acid ester groups may not be contained, and the content may be 0% by mass or more.
• the content ratio by number of fatty acid ester groups can be measured by the same method as the measurement method described in the section on sucrose fatty acid esters below.
• the sugar fatty acid ester is not particularly limited as long as it is usable in food, and examples thereof include sucrose fatty acid esters, sorbitan fatty acid esters, glucose esters, etc., and among these, sucrose fatty acid esters are preferred from the viewpoint of easy availability.
• the sugar-based surfactant may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that 60% by mass or more of the sugar-based surfactant is sucrose fatty acid ester when the total amount of the sugar-based surfactant is 100% by mass.
• This ratio is more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of suppressing the stickiness of the obtained coating and increasing the water vapor barrier property and oxygen barrier property.
• the sugar-based surfactant may be sucrose fatty acid ester alone, and therefore the above ratio may be 100% by mass or less.
• the sucrose fatty acid ester used in the present composition may be any known sucrose fatty acid ester, provided that at least one of the eight hydroxyl groups of sucrose forms an ester structure with a fatty acid.
• the constituent fatty acids of the sucrose fatty acid ester are preferably edible fats and oils.
• the number of carbon atoms of the constituent fatty acid of the sucrose fatty acid ester is not particularly limited, but is preferably from 12 to 22, more preferably from 12 to 18, and even more preferably from 14 to 18. When the number of carbon atoms is within the above range, the stickiness of the resulting coating can be suppressed.
• the constituent fatty acid of the sucrose fatty acid ester may be a saturated or unsaturated fatty acid, but a saturated fatty acid is preferred from the viewpoint of easily becoming solid at room temperature (20 to 25° C.) and suppressing stickiness of the resulting coating.
• examples of such acids include lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, etc., and among these, lauric acid, myristic acid, palmitic acid, and stearic acid, which are saturated fatty acids having from 12 to 18 carbon atoms, are preferred, and myristic acid, palmitic acid, and stearic acid, which are saturated fatty acids having from 14 to 18 carbon atoms, are more preferred. These saturated fatty acids may be used alone or in combination of two or more.
• the constituent fatty acids of the sugar fatty acid ester do not need to be all the same, and it is sufficient that 60% by mass or more of the constituent fatty acids in the sucrose fatty acid ester are the above-mentioned suitable constituent fatty acids. From the viewpoint of suppressing the stickiness of the obtained coating, this ratio is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. There is no particular limit to the upper limit, but it is sufficient that it is 100% by mass or less.
• the fatty acid composition of the sucrose fatty acid ester can be measured by isolating the sucrose fatty acid ester from the composition, derivatizing it, and then subjecting it to gas chromatography.
• the sucrose fatty acid ester has 1 to 8 fatty acid ester groups. From the viewpoint of forming a coating film using an aqueous solvent, when the total amount of sucrose fatty acid esters is taken as 100 mass%, it is preferable that the sucrose fatty acid esters contain 50 mass% or more of sucrose fatty acid esters (monoesters, diesters, or triesters) having 3 or less fatty acid ester groups, more preferably 60 mass% or more, and even more preferably 70 mass% or more. There is no particular limit to the upper limit, but it is sufficient as long as it is 100 mass% or less.
• sucrose fatty acid esters having 6 or more fatty acid ester groups are preferably contained in an amount of 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• Sucrose fatty acid esters having 6 or more fatty acid ester groups may not be contained, and the content may be 0% by mass or more.
• the content ratio of each fatty acid ester group can be measured after isolating the sugar fatty acid ester from the composition according to the METHOD OF ASSAY described in Residue Monograph prepared by the meeting of the Joint FAO/WHO Expert Committee on Food Additives (JECFA), 84th meeting 2017 "Sucrose Esters of Fatty Acids” and Prepared at the 71st JECFA (2009) and published in FAO JECFA Monographs 7 (2009) "Sucrose Oligoesters Type I" and "Sucrose Oligoesters Type II".
• JECFA Joint FAO/WHO Expert Committee on Food Additives
• a sample is dissolved in a certain amount of tetrahydrofuran (stabilizer-containing GPC or industrial grade), and the insoluble matter is removed using a 0.5 ⁇ m membrane filter to obtain a solution, which is used as a measurement sample and subjected to high performance liquid chromatography under the following conditions:
• the composition ratio is calculated by individually calculating the peak areas of the monoester to triester and the combined peak area of the tetraester and above, and then calculating the ratio to the total peak area of all peaks detected up to 43 minutes.
• the peak area corresponds to the area from the start point (rising point) to the end point (falling point) of each peak.
• HLC-8320GPC Detector Differential refractometer (manufactured by Tosoh Corporation) Column: TSK-gel G1000HXL, G2000HXL, G3000HXL, G4000HXL (manufactured by Tosoh Corporation) Column temperature: 40°C Detector temperature: 40°C Eluent: Tetrahydrofuran (stabilized GPC or industrial grade) Flow rate: 0.8ml/min Injection volume: 80 ⁇ l Measurement time: 50 minutes (area ratio is calculated based on all peaks detected up to 43 minutes)
• the composition ratio of tetraester to octaester is calculated by calculating the peak area of each of the tetraester to octaester individually, calculating the ratio of the peak area to the total peak area of the tetraester to octaester, and dividing the area ratio of tetraesters and above determined in the above ⁇ Measurement of monoesters to triesters, and tetraesters and above>> proportionately based on the area ratio of tetraesters to octaesters.
• the peak area corresponds to the area from the start point (rising point) to the end point (falling point) of each peak. When two or more peaks are adjacent to each other and the start and end points are unknown, the points where the data between the peaks is smallest are set as the start and end points, and the area is calculated.
• sucrose fatty acid esters Commercially available products of the sucrose fatty acid esters include "Ryoto (registered trademark) Sugar Ester S-370", “Ryoto (registered trademark) Sugar Ester S-570", “Ryoto Sugar Ester S-970", “Ryoto (registered trademark) Sugar Ester S-1170", “Ryoto (registered trademark) Sugar Ester S-1570", “Ryoto (registered trademark) Sugar Ester S-1670", “Ryoto (registered trademark) Sugar Ester P-170", “Ryoto (registered trademark) Sugar Ester P-1670", “Ryoto (registered trademark) Sugar Ester M-1695", “Ryoto (registered trademark) Sugar Ester O-170", “Ryoto (registered trademark) Sugar Ester Examples of such sugar esters include “RYOTO (registered trademark) Sugar Ester L-1570", “RYOTO (registered trademark) Sugar Ester L-195", “RYOTO (registere
• sucrose fatty acid ester that is solid at 0° C. or higher, since this can broaden the range of application of the coating composition of the present invention in terms of industrial use.
• sucrose fatty acid esters may be used alone or in combination of two or more.
• the sucrose fatty acid ester is preferably crystalline from the viewpoints of suppressing stickiness of the resulting coating and improving the water vapor barrier property and oxygen barrier property. Moreover, from the viewpoint of suppressing stickiness of the resulting coating, the sucrose fatty acid ester preferably contains 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more of components that become solid at room temperature (20 to 25° C.). The sucrose fatty acid ester may be composed only of components that become solid at room temperature (20 to 25° C.), and therefore the above ratio may be 100% by mass or less.
• the sucrose fatty acid ester is preferably crystalline, from the viewpoints of suppressing stickiness of the resulting coating and enhancing the water vapor barrier property.
• the crystal melting peak temperature is preferably 40° C. or higher and 80° C. or lower, and more preferably 45° C. or higher and 70° C. or lower.
• the crystal melting peak temperature is 40° C. or higher, the stickiness of the resulting coating film can be suppressed.
• the crystal melting peak temperature is 80° C. or lower, the heating can be reduced when dissolving in an aqueous solvent, and the productivity is improved.
• the crystalline melting peak temperature is the temperature at which a crystalline melting peak is detected in differential scanning calorimetry (DSC) measured by placing 1 mg of sucrose fatty acid ester in an aluminum pan and initially heating the pan from 30° C. to 100° C. at a heating rate of 10° C./min.
• DSC differential scanning calorimetry
• the sum of the peak areas in the above temperature range is 50% or more of the sum of the peak areas in the entire temperature range.
• the composition may contain other fatty acid esters as long as the effects of the present invention are not impaired.
• the other fatty acid esters are not particularly limited as long as they are usable in foods, and examples thereof include sorbitan fatty acid esters and glucose esters.
• Glycerol fatty acid esters are formed by esterifying glycerol with a fatty acid.
• fatty acids constituting the glycerin fatty acid ester include the same fatty acids as those constituting the sucrose fatty acid ester.
• the content of glycerin fatty acid esters (monoesters) having one fatty acid ester group is usually 5% by mass or more when the total amount of glycerin fatty acid esters is taken as 100% by mass, from the viewpoints of dispersibility in aqueous solvents and viscosity and handling of the composition. 10% by mass or more is preferable, 20% by mass or more is more preferable, 30% by mass or more is even more preferable, and 40% by mass or more is particularly preferable. Outside this range, 50% by mass or more is preferable, 60% by mass or more is more preferable, 70% by mass or more is even more preferable, and 80% by mass or more is particularly preferable. There is no particular upper limit, but it is sufficient as long as it is 100% by mass or less.
• the amount of glycerin fatty acid ester (diester) containing two fatty acid ester groups depends on the amount of monoester and triester, and is not particularly limited.
• the content of glycerin fatty acid esters (triesters) having three fatty acid ester groups is preferably 50% by mass or less, more preferably 40% by mass or more, even more preferably 30% by mass or more, particularly preferably 20% by mass or more, and most preferably 10% by mass or more, when the total amount of glycerin fatty acid esters is taken as 100% by mass, from the viewpoints of dispersibility in aqueous solvents, viscosity of the composition, and ease of handling.
• the total amount of glycerin fatty acid esters having one fatty acid ester group (monoester) and fatty acid esters having two fatty acid ester groups (diester) is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more.
• the upper limit is no particular limit to the upper limit, but it is sufficient as long as it is 100 mass% or less.
• the proportion of monoester in the total of monoester and diester is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 80% by mass. There is no particular upper limit, but it is sufficient as long as it is 100% by mass or less.
• the types and amounts of fatty acids can be analyzed using column chromatography, gas chromatography, thin layer chromatography, high performance liquid chromatography, colorimetric analysis, etc.
• the mass ratio (solid content) of the sucrose fatty acid ester to the total mass of the sucrose fatty acid ester and the glycerin fatty acid ester is preferably 1% or more, more preferably 5% or more, even more preferably 10% or more, and particularly preferably 20% or more. Moreover, the ratio is less than 100%. Within this range, the applicability of the composition is good, and the coat appearance after application to fruits and vegetables is good.
• the mass ratio of the sucrose fatty acid ester and the glycerin fatty acid ester is preferably 1/99 to 99/1, more preferably 5/95 to 99/1, even more preferably 10/90 to 98/2, particularly preferably in the range of 20/80 to 97/3, and most preferably in the range of 20/80 to 80/20.
• the composition may be solvent-free, but preferably contains a solvent from the viewpoint of application efficiency.
• the solvent preferably contains an aqueous solvent.
• the aqueous solvent constituting the coating composition (coating composition) is water or a mixed solvent of one or more water-soluble organic solvents and water.
• the water-soluble organic solvent include alcohols such as ethanol, isopropanol, ethylene glycol, and glycerin.
• the solvent may contain an organic solvent such as the above-mentioned alcohol in addition to water.
• the content of the organic solvent in the aqueous solvent is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less.
• the coating composition of the present invention may contain other components in amounts that do not impair the function of the coating composition of the present invention.
• examples of other components include a pH adjuster.
• As the pH adjuster for example, acetic acid, lactic acid, citric acid, ammonia, etc. can be used.
• the ratio of the endothermic peak total area A1 in the range of 0°C to 40°C to the endothermic peak total area A2 in the range of 0°C to 80°C or less may be 50% or less.
• the ratio is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less.
• the ratio may be 0%.
• the rate of phase change of the coating film formed on the coating composition is reduced within the practical temperature range for storing, transporting, and selling fruits and vegetables that are not frozen, and no phase change that affects the properties of the coating film occurs.
• the freshness-preserving functions such as water vapor barrier properties and oxygen barrier properties described later can be maintained.
• the peak area is the area from the start point (rising point) to the end point (falling point) of each peak.
• the temperature range for calculating A1 is preferably 0° C. or more and 35° C. or less, more preferably 0° C. or more and 30° C. or less, and even more preferably 0° C. or more and 25° C. or less.
• A1 and A2 there may be cases where multiple peaks exist within each temperature range for which the total area is calculated, or where only a portion of a peak falls within that temperature range. In such cases, for all peaks existing within that temperature range, the total area of only the portion that falls within that temperature range is calculated. For example, if one broad peak exists between 0 and 50°C, only the portion between 0 and 40°C is calculated as A1 .
• the surfactant used in the coating composition of the present invention it is considered that there is almost no peak in the temperature range exceeding 80°C, and therefore, for A2 , it is considered that it is not necessary to consider the range exceeding 80°C.
• Differential scanning calorimetry with a measurement temperature range of 0° C. or higher is carried out under the following conditions.
• Measuring device Differential scanning calorimeter Measurement method: Heat flux method Temperature: 25°C ⁇ 0°C ⁇ 100°C Temperature increase/decrease rate: 10°C/min Atmosphere: Nitrogen Sample preparation: The coating composition is placed in an empty aluminum pan so that the dry solid content is 1 mg, and the pan is left to stand at room temperature to dry. It is confirmed that the weight change from the previous day is 1% or less, and a measurement sample is obtained.
• the coating composition according to the present invention may have a ratio of the total exothermic peak area A3 to the total endothermic peak area A2 from 0°C to 80°C of 50% or less in differential scanning calorimetry with a measurement temperature range of -80°C or higher.
• the stickiness of the coating film formed from the coating composition within the temperature range in which fruits and vegetables not stored frozen are stored, transported, and sold can be suppressed, improving handleability, and further improving freshness-retaining functions such as water vapor barrier properties and oxygen barrier properties described below.
• the peak area is the area from the start point (rising point) to the end point (falling point) of each peak.
• the exothermic peak is considered to indicate the behavior of phase change in which a component that has not become solid becomes solid, or the behavior of crystallization in which a component that has not crystallized becomes crystallization.
• the endothermic peak observed at 0°C or higher is considered to be a peak derived from the behavior of phase change in which all components that can become solid in the coating formed from the coating composition become solid, for example, the behavior of melting of all crystallizable components of the coating that have crystallized.
• the ratio of the total area A3 of the exothermic peaks to the total area A2 of the endothermic peaks at 0°C or higher and 80°C or lower is considered to indicate the ratio of components that have not become solid, for example, have not crystallized, at 0°C or higher in the coating formed from the coating composition.
• the ratio is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less. Note that some exothermic peaks observed by the measurement method described below may be observed during heating. This is considered to indicate the behavior of components that have been in a supercooled state becoming solid, for example, crystallizing.
• A2 and A3 there may be cases where multiple peaks exist within the respective temperature ranges for which the total area is calculated. In that case, for all peaks existing within the temperature range, all areas of only the parts belonging to the temperature range are calculated. Although unlikely, one peak may exist within a temperature range including 0°C. In that case, the peak area is judged to be a part or all of A2 and A3 depending on whether it is an endothermic peak or an exothermic peak. Since it is considered that there is almost no peak in the temperature range below -80°C and above 80°C for the surfactant used in the coating composition of the present invention, it is considered that there is no need to consider the range below -80°C and above 80°C for A2 and A3 .
• Differential scanning calorimetry with a measurement temperature range of ⁇ 80° C. or higher is carried out under the following conditions.
• Measuring device Differential scanning calorimeter
• Measuring method Heat flux method Temperature: 25°C ⁇ -80°C ⁇ 100°C Temperature increase/decrease rate: 10°C/min
• Atmosphere Nitrogen Sample preparation: Place the coating composition in an empty aluminum pan so that the dry solid content is 1 mg, leave it to stand at room temperature and dry. Confirm that the weight change from the previous day is 1% or less, and obtain a measurement sample.
• the shear viscosity of the present composition at a shear rate of 1 s -1 is preferably 8000 mPa ⁇ s or less. More preferably, it is 4000 mPa ⁇ s or less, even more preferably, it is 2000 mPa ⁇ s or less, particularly preferably, it is 1000 mPa ⁇ s or less, and most preferably, it is 500 mPa ⁇ s or less. By being equal to or less than the upper limit, the present composition can be applied uniformly.
• the lower limit of the shear viscosity is preferably 0.1 mPa ⁇ s or more.
• it is 1 mPa ⁇ s or more, even more preferably, it is 5 mPa ⁇ s or more, particularly preferably, it is 10 mPa ⁇ s or more, and most preferably, it is 50 mPa ⁇ s or more. Among them, it is more preferably 80 mPa or more, and even more preferably, it is 100 mPa ⁇ s or more.
• the non-volatile component concentration in the present composition is not particularly limited, but is usually 0.1 mass% or more. It is preferably 0.2 mass% or more, more preferably 0.3 mass% or more, even more preferably 0.5 mass% or more, particularly preferably 1 mass% or more, and preferably 2 mass% or more. Furthermore, it is more preferably 2.5 mass% or more, even more preferably 3.0 mass% or more, particularly preferably 3.5 mass% or more, and most preferably 4.0 mass% or more. In particular, by being 1 mass% or more, a sufficient film thickness can be ensured when a coating is formed, so that gas barrier properties such as water vapor and oxygen can be easily expressed, and the storage stability of fruits and vegetables can be fully exhibited.
• the upper limit of the non-volatile component concentration in the composition is not particularly limited, but is usually 60% by mass or less. 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is even more preferable, 20% by mass or less is more particularly preferable, and 10% by mass or less is most preferable.
• the non-volatile component concentration refers to the concentration of non-volatile components excluding the solvent contained in the composition.
• the pH of the present composition is preferably from 4 to 10, and more preferably from 4 to 8, from the viewpoint of safe application to foods.
• the coating liquid composition of the present invention is preferably produced by mixing a sugar surfactant, a glycerin fatty acid ester and a solvent, heating the mixture, and then cooling. This method is believed to increase the uniformity of the mixture of the sugar surfactant and the glycerin fatty acid ester in the aggregate formed by the sugar surfactant and the glycerin fatty acid ester, thereby forming a dense film and further reducing gas permeability.
• the uniformity of the coating liquid composition can be improved by using a sugar fatty acid ester and a glycerin fatty acid ester in combination.
• the coated fruits or vegetables of the present invention are fruits or vegetables that are coated with the above-mentioned coating composition to form a coating, which inhibits the respiration and evaporation of water from the fruits or vegetables, thereby maintaining the freshness of the fruits or vegetables.
• the fruits and vegetables to which the composition is applied refer to vegetables, fruit trees, and the like, and specifically include citrus fruits such as oranges, grapefruits, and mandarins; pome fruits such as quince, pears, loquats, and apples; stone fruits such as peaches, apricots, plums, plums, and cherry blossoms; small fruits such as berries, including blackberries, raspberries, blueberries, and grapes; root vegetables such as daikon radishes, carrots, ginger, and burdock; tubers such as sweet potatoes, taro, and potatoes; onions, chives, garlic, and camellia.
• citrus fruits such as oranges, grapefruits, and mandarins
• pome fruits such as quince, pears, loquats, and apples
• stone fruits such as peaches, apricots, plums, plums, and cherry blossoms
• small fruits such as berries, including blackberries, raspberries, blueberries, and grapes
• root vegetables such as dai
• bulbs such as onions and squash; cucumbers, zucchini, bitter melon, pumpkin, melon, watermelon, and other gourds; Solanaceae fruit vegetables such as tomatoes, cherry tomatoes, eggplant, bell peppers, and chili peppers; Brassica vegetables such as broccoli, cauliflower, and zha cai; leafy vegetables such as bok choy, takana, cabbage, Chinese cabbage, lettuce, and chrysanthemum; stem vegetables such as butterbur, asparagus, bracken, fern, and butterbur, and mushrooms such as shiitake mushrooms, king oyster mushrooms, bunashimeji mushrooms, enoki mushrooms, and maitake mushrooms.
• the coating in the present invention is formed by volatilizing the solvent from the composition, and therefore the types and composition ratios of the sugar-based surfactant and glycerin fatty acid ester in the coating, as well as the preferred contents of the non-volatile components, are the same as those described above.
• the coating in the present invention preferably has water vapor barrier properties and/or oxygen barrier properties in order to suppress respiration and evaporation of moisture.
• the coating is preferably edible.
• the coating film formed by the coating liquid composition of the present invention has a water vapor transmission rate per 1 ⁇ m at 30 ° C. and 80% RH of preferably 0.1 g / (m 2 ⁇ day ⁇ atm) or more, more preferably 0.5 g / (m 2 ⁇ day ⁇ atm) or more, and even more preferably 1.0 g / (m 2 ⁇ day ⁇ atm) or more.
• It is preferably 100 g / (m 2 ⁇ day ⁇ atm) or less, more preferably 80 g / (m 2 ⁇ day ⁇ atm) or less, even more preferably 60 g / (m 2 ⁇ day ⁇ atm) or less, and particularly preferably 40 g / (m 2 ⁇ day ⁇ atm) or less.
• it is preferably 20 g / (m 2 ⁇ day ⁇ atm) or less, more preferably 17 g / (m 2 ⁇ day ⁇ atm) or less, and even more preferably 15 g / (m 2 ⁇ day ⁇ atm) or less.
• the water vapor transmission rate can be measured by a differential pressure method using a water vapor transmission rate measuring device DELTAPERM based on JIS K7129-5. More specifically, the water vapor transmission rate measured when the composition is coated on a polyethylene terephthalate film having a thickness of 50 ⁇ m under conditions of 30° C. and 80% RH is converted to transmission rate per ⁇ m by the following formula.
• the coating film formed by the coating liquid composition of the present invention has an oxygen permeability per 1 ⁇ m at 25° C. and 50% RH of preferably 0.1 cc/(m 2 ⁇ day ⁇ atm) or more, more preferably 0.5 cc/(m 2 ⁇ day ⁇ atm) or more, and even more preferably 1.0 cc/(m 2 ⁇ day ⁇ atm) or more.
• 100 cc/( m2 ⁇ day ⁇ atm) or less is more preferable
• 90 cc/( m2 ⁇ day ⁇ atm) or less is even more preferable
• 50 cc/( m2 ⁇ day ⁇ atm) or less is particularly preferable.
• the oxygen transmission rate can be measured by an isobaric method using an oxygen transmission rate measuring device OX-TRAN 2/21 (manufactured by MOCON Co., Ltd.) based on JIS K7126-2. More specifically, the measured oxygen transmission rate when the film is coated on a polyethylene terephthalate film having a thickness of 50 ⁇ m under conditions of 25° C. and 50% RH is converted into transmission rate per ⁇ m by the following formula.
• Edible means that it can be used for food. From the viewpoint of safety, it is preferable to make a compound approved as a food additive edible by using it in a dosage that satisfies the requirements.
• the coating of the present invention is preferably crystalline from the viewpoints of suppressing stickiness and enhancing water vapor barrier properties.
• the crystal melting peak temperature of the coating of the present invention is preferably from 40° C. to 80° C., more preferably from 45° C. to 70° C. When the crystal melting peak temperature is 40° C. or higher, the stickiness of the resulting coating can be suppressed.
• the crystal melting peak temperature is the temperature at which a crystal melting peak is detected during the initial temperature rise from 30°C to 100°C in differential scanning calorimetry (DSC) measured at a heating rate of 10°C/min.
• the sum of the peak areas in the above temperature range is 50% or more of the sum of the peak areas in the entire temperature range.
• a coating may be formed on any substrate and measured, or only the coating may be measured.
• the substrate may be a polyethylene terephthalate film or a glass plate.
• the average thickness of the coating of the coated fruit or vegetable is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m.
• the average thickness is 0.1 ⁇ m or more, the respiration of the fruit or vegetable and the evaporation of water are sufficiently suppressed.
• the coating thickness is 10 ⁇ m or less, the coating can be formed while maintaining the texture of the fruit or vegetable as a food. In the present invention, the coating thickness does not need to be uniform throughout the food product.
• the average thickness of the coating can be determined by observing the cross section of the coated fruit or vegetable under a microscope, randomly selecting 10 or more points and measuring the thickness, and averaging the measured thickness.
• the method for preserving the freshness of fruits and vegetables of the present invention comprises the step of covering the fruits and vegetables with the present composition.
• the process of covering with the present composition is not particularly limited as long as it is a process of covering fruits or vegetables with the present composition, and examples thereof include direct application methods such as brush coating and curtain coating; immersion methods such as impregnation coating; and spraying methods such as spray coating.
• the immersion method and the spraying method are preferred from the viewpoint of being able to relatively uniformly coat fruits or vegetables having a three-dimensional shape and from the viewpoint of productivity.
• the composition When covering fruits or vegetables with the composition, the composition may be applied to only a part of the fruits or vegetables, or may be applied to the entirety of the fruits or vegetables. By applying the composition to the entirety, the freshness of the fruits or vegetables can be effectively maintained. On the other hand, from the viewpoint of shortening the drying time of the composition and increasing the efficiency of the coating formation treatment, the composition may be applied to only a part of the fruits or vegetables.
• the coating area is preferably 10% or more of the surface area of the fruit or vegetable, more preferably 25% or more, even more preferably 40% or more, and even more preferably 50% or more.
• a part of the applied composition may be removed.
• the method for removing the composition is not particularly limited, but examples thereof include removal by air pressure using an air dryer. By removing the composition, insufficient drying of the part where an excessive amount of the composition is applied can be prevented. For information on coating methods, see “Coating Methods" published by Maki Shoten in 1979 by Harasaki Yuji.
• the coating may be dried to remove the aqueous solvent. Drying methods include, for example, static drying, air drying, and heat drying. From the viewpoint of maintaining the freshness of fruit or vegetables, a method of drying by leaving the composition statically at room temperature (20 to 25°C) or a method of air drying at room temperature are preferred.
• ⁇ Differential scanning calorimetry at temperatures above -80°C> Differential scanning calorimetry with a measurement temperature range of ⁇ 80° C. or higher was carried out under the following conditions.
• the coating solution prepared in each of the Examples and Comparative Examples was applied to an avocado by dipping, and the appearance defects resulting from the coating solution remaining on the avocado skin after drying were visually evaluated according to the following criteria.
• Weight retention rate Using the weight of the avocado before storage (day 0) as the standard, the weight retention rate ((weight after storage/weight on day 0) x 100 (%)) after storage for 3, 4, and 5 days at 25°C and 50% RH was calculated.
• weight loss rate The weight of the avocado before storage (day 0) was used as the standard, and the weight loss rate after storage for 4 days at 25° C. and 50% RH was calculated (100 ⁇ (weight after storage/weight on day 0) ⁇ 100(%)).
• the load (N) was measured when a cylindrical plunger with a diameter of 5 mm was pressed 3 mm into the avocado at a speed of 60 mm/min.
• Three avocados stored at 25°C and 50% RH for four days were used for the measurement, and measurements were taken at three different points near the equator for each avocado, and the arithmetic mean of the obtained values was taken as the fruit firmness.
• Rikemal (registered trademark) S-100P main component: glycerin monostearate, HLB: 4.3, melting point 63-68°C, monoester content: 95% or more
• M-100 Glycerin fatty acid ester, Riken Vitamin Co., Ltd.
• M-100 main component: glycerin monocaprylate, HLB: 7.0, melting point about 31°C, monoester content: 85% or more
• M-1695 Sucrose myristate ester, Mitsubishi Chemical Corporation "Ryoto (registered trademark) Sugar Ester M-1695", HLB: about 16, monoester content: about 80%, bound fatty acid purity: about 20%
• MCT oil Medium chain fatty acid triacylglycerol (tri (caprylic acid / capric acid) glyceryl) manufactured by Nisshin Oillio Group Co., Ltd. Tannic acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• Example 1 Method of preparing coating liquid
• a coating liquid (coating composition) was prepared by dispersing glycerin fatty acid ester (S-100P) and sucrose fatty acid ester (S-1170) in a water solvent (ion-exchanged water) at 73°C for 30 minutes, leaving the mixture at room temperature of 20°C, and then cooling it to 25°C.
• the content of each material is as shown in Table 1.
• the evaluation results are shown in Table 1.
• Example 2 A coating solution was prepared in the same manner as in Example 1, except that the contents of glycerin fatty acid ester and sucrose fatty acid ester were changed as shown in Table 1. The evaluation results are shown in Table 1.
• Comparative Example 1 A coating solution was prepared in the same manner as in Example 1, except that Rikemal (registered trademark) S-100P was used as the glycerin fatty acid ester and no sucrose fatty acid ester was added. The coating solution was separated from the solvent. Subsequent evaluations could not be measured.
• Example 5 in which the mass ratio of sucrose fatty acid ester and glycerin fatty acid ester is outside the scope of the present invention, the coating appearance was poor, but the freshness preservation effect was exhibited without any problems.
• a coating solution without sucrose fatty acid ester was used, the viscosity was high and the shear rate could not be measured, as shown in Comparative Example 1. Therefore, a coating could not be formed on the avocado.
• Example 6 to 11 Comparative Examples 2 to 4
• a coating solution was prepared in the same manner as in Example 1, except that the sugar fatty acid ester and glycerin fatty acid ester were used with the ingredients and compositions shown in Table 2.
• the state of the coating solution, the viscosity of the coating solution, the state of the coating film, and the freshness retention of the coated avocado were evaluated, and the results are shown in Table 2.
• Example 8 In the aqueous coating composition in Example 8 in which S-1170 was replaced with the equivalent F-110, the A 3 /A 2 ratio at temperatures of -80° C. or higher was 49%.
• Example 10 In the differential scanning calorimetry of Example 10 at -80°C or higher, there was an exothermic peak of 4.885 J/g having a peak top at 1.1°C in the range of 2°C to -1°C during cooling, two exothermic peaks of 32.9 J/g having a peak top at -29.6°C in the range of -29°C to -32°C, and an exothermic peak of 32.07 J/g having a peak top at -27.1°C in the range of -27°C to -25°C during heating.
• Example 11 In the differential scanning calorimetry of Example 11 at -80°C or higher, there was an exothermic peak of 4.358 J/g having a peak top at 1.8°C in the range of 2°C to -2°C during cooling, and two exothermic peaks of 30.58 J/g having a peak top at -29.7°C in the range of -29°C to -32°C during cooling, and there was an exothermic peak of 28.11 J/g having a peak top at -26.4°C in the range of -29°C to -24°C during heating.
• the coating composition of the present invention is in a uniform state without precipitation or separation, and therefore the coating treatment can be stably performed, and the avocado coated with the coating composition of the present invention has a good coating appearance when coated, and shows good results in weight retention rate, skin color, and fruit firmness after storage for 4 days. From the results of Examples 1 to 11 and Comparative Examples 3 and 4, it was found that the low ratio of triester in the coating composition makes it a stable coating composition liquid.
• the coating compositions of Examples 6, 7, 9, and 10 were in a uniform state with good fluidity, whereas the coating composition of Comparative Example 1 was in a non-uniform state without good fluidity.
• the coating composition exhibits physical properties suitable for use in coating by blending a certain amount of sucrose fatty acid ester with glycerin fatty acid ester. This is believed to be because the glycerin fatty acid ester, which alone could not become a stable coating liquid, was changed to a state usable as a coating liquid by mixing it with a certain amount of sucrose fatty acid ester having a similar structure and a fatty acid ester in its structure.
• sucrose fatty acid ester is 10% by mass or more in the mass ratio of sucrose fatty acid ester and glycerin fatty acid ester in the coating liquid composition
• the effect of suppressing ripening such as change in skin color and decrease in hardness of avocado is enhanced.
• the coating composition of the present invention can be particularly suitably used for fruits and vegetables.
• the present invention by covering fruits and vegetables with a coating that is highly safe and has a high water vapor barrier property, it is possible to suppress evaporation of moisture from the fruits and vegetables and maintain their freshness for a long period of time.
• a coating that is highly safe and has a high water vapor barrier property it is possible to suppress evaporation of moisture from the fruits and vegetables and maintain their freshness for a long period of time.
• since the freshness of the fruits and vegetables is maintained for a long period of time there is no need for farmers to ship the fruits and vegetables earlier than necessary when harvesting them, and there is also the advantage that consumers can obtain fruits and vegetables with excellent freshness, making this a technology with high industrial value.

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