Gas hydrate-containing ice and frozen desserts containing that gas hydrate-containing ice

Abstract

To provide a novel gas hydrate-containing ice with improved hydrate stability. [Solution] Gas hydrate-containing ice in which the coefficient of variation of the Brix values ​​of multiple gas hydrate-containing ice pieces is 0.4 or less when the gas hydrate-containing ice is divided into multiple pieces.

Description

Technical Field

[0001] The present invention relates to gas hydrate-containing ice and frozen desserts containing the gas hydrate-containing ice.

Background Art

[0002] In recent years, the development of gas hydrate-containing ice as a new food material has been underway. A gas hydrate generally refers to an ice-like solid crystal formed by a gas such as methane, ethane, and carbon dioxide and ice.

[0003] The gas hydrate-containing ice produced from a solution is manufactured, for example, by the method described in Patent Document 1. The method described in Patent Document 1 is a so-called batch method, in which hydrate is generated in a slurry production container, and the sherbet-like slurry containing the generated hydrate is cooled to produce gas hydrate-containing ice.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the above prior art, the sherbet-like slurry containing acidulant-containing CO2 hydrate produced by the batch method is sent to a squeezer through a pipe, but some of the solution remains in the slurry production container. The inventors of the present invention found that when attempting to continuously produce gas hydrate-containing ice by the batch method, the concentration of the solution in the slurry production container becomes high due to the remaining solution, and the produced gas hydrate-containing ice becomes non-uniform. They also found that the storage stability of the gas hydrate produced by the batch method is low.

[0006] A decrease in the storage stability of gas hydrates can affect the palatability of ice containing gas hydrates. Therefore, the object of the present invention is to provide a novel gas hydrate-containing ice with improved hydrate stability.

[0007] The present invention, which solves the above problems, is as follows [1] to [5]. [1] Gas hydrate-containing ice in which the coefficient of variation of the Brix values ​​of the multiple gas hydrate-containing ice pieces, when the gas hydrate-containing ice is divided into multiple pieces, is 0.4 or less.

[0008] [2] Gas hydrate-containing ice as described in [1], wherein the gas content is 3% by weight or more.

[0009] [3] Gas hydrate-containing ice as described in [1] or [2], made with a flavored solution.

[0010] [4] Gas hydrate-containing ice as described in any of [1] to [3], containing one or more components selected from the group consisting of flavorings, sweeteners, acidulants, salts, emulsifiers, inorganic substances, and amino acids.

[0011] [5] A frozen dessert containing ice containing gas hydrate as described in any of [1] to [4]. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a novel gas hydrate-containing ice with improved hydrate stability. [Modes for carrying out the invention]

[0013] In this invention, "gas hydrate-containing ice" refers to ice obtained by freezing a slurry containing gas hydrate, which is produced by mixing gas and a solution and applying low temperature and high pressure, as well as unreacted solution that was not used to produce the gas hydrate. In other words, gas hydrate-containing ice is a state in which the gas hydrate is surrounded by ice made from the solution. Since only water in the solution is used to form gas hydrates, the concentration of unreacted solution that was not used to form gas hydrates becomes higher than the concentration before gas hydrate formation.

[0014] Gas hydrates are solid crystals in the form of ice formed from gases such as methane, ethane, and carbon dioxide. Gas hydrates can be produced by subjecting gases and water (including those in solution) to low temperature and high pressure conditions. The aforementioned gas is not particularly limited as long as it can produce a gas hydrate, but it is preferably a gas that can be used in food. Examples include carbon dioxide, helium, hydrogen, oxygen, nitrogen, nitrous oxide, and argon. Examples of gas hydrates produced include carbon dioxide hydrate, helium hydrate, and oxygen hydrate.

[0015] The gas hydrate in this invention is preferably carbon dioxide hydrate. Carbon dioxide hydrate can be produced, for example, by mixing carbon dioxide with a solution and cooling it at a temperature of 0 to 10°C under a pressure of 1 to 5 MPa, preferably 1.3 to 3.2 MPa.

[0016] In the present invention, gas hydrate-containing ice can be produced by using a circulating gas hydrate-containing ice production apparatus to mix a raw material solution and a raw material gas, applying low temperature and high pressure to generate gas hydrate, and freezing a slurry containing unreacted raw material solution that was not used to generate the gas hydrate. In this case, when a flavored aqueous solution is used as the solution for producing gas hydrate-containing ice, flavored gas hydrate-containing ice can be produced.

[0017] The solution in the present invention is not particularly limited as long as it can generate gas hydrate, but it is an aqueous solution containing components such as flavors, sweeteners, acidulants, emulsifiers, stabilizers, salts, amino acids, coloring agents, dietary fibers, thickening polysaccharides, vitamins, minerals, inorganic substances, and / or fruit juices. Preferably, it is a flavored aqueous solution containing one or more components selected from the group consisting of flavors, sweeteners, acidulants, salts, emulsifiers, inorganic substances, and amino acids.

[0018] The inorganic substances in the present invention preferably refer to inorganic elements and their compounds contained in trace amounts in each raw material and water, such as magnesium, iron, copper, zinc, manganese, etc.

[0019] The gas hydrate-containing ice in the present invention has a coefficient of variation of the Brix values of the plurality of gas hydrate-containing ice when the gas hydrate-containing ice is divided into a plurality of pieces of 0.4 or less. The coefficient of variation of the Brix value is preferably 0.35 or less, more preferably 0.3 or less, still more preferably 0.25 or less, even more preferably 0.2 or less, and most preferably 0.15 or less.

[0020] The coefficient of variation is obtained by the following formula (1). Coefficient of variation = standard deviation / average ···(1)

[0021] The Brix value of the gas hydrate-containing ice can be calculated from the solution obtained by melting the gas hydrate-containing ice. Examples of the method for calculating the Brix value of the gas hydrate-containing ice include a method of calculating the Brix value at 20°C using a refractometer (manufactured by ATAGO, model: RX-5000i).

[0022] In this specification, dividing the gas hydrate-containing ice into multiple parts includes dividing the gas hydrate-containing ice into multiple ice blocks by crushing it, and dividing multiple gas hydrate-containing ice into units of several pieces. "Dividing multiple gas hydrate-containing ice into units of several pieces" means dividing separate gas hydrate-containing ice before crushing into units of one or more pieces. In the present invention, the gas hydrate-containing ice is preferably divided into 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 10 or more. In a preferred embodiment of the present invention, the coefficient of variation of the Brix value of each ice block containing a plurality of gas hydrates is 0.4 or less.

[0023] The gas hydrate-containing ice in this invention not only improves the non-uniformity of gas hydrate-containing ice produced in batches, but also exhibits superior storage stability of the gas hydrate when stored at -25°C (defrosted twice a day) for one week.

[0024] In this invention, defrosting is performed for 30 minutes every 12 hours. Specifically, defrosting is carried out based on a program that raises the surface temperature inside the freezer to 5°C and then lowers the temperature back down to -25°C.

[0025] In the present invention, the storage stability when stored at -25°C (defrosted twice a day) for one week can be evaluated by the remaining percentage calculated using the following formula (2), where S0 is the average hydrate percentage at the time of creating or obtaining the gas hydrate-containing ice, and S1 is the average hydrate percentage after storing at -25°C (defrosted twice a day) for one week. Survival rate (%) = 100×S1 / S0 (2)

[0026] The hydrate ratio of gas hydrate-containing ice refers to the ratio of the weight of gas hydrate to the weight of the ice mass, where gas hydrate-containing ice mass is considered to be 1. While there are no particular limitations on the method for calculating the hydrate ratio of gas hydrate-containing ice, it can be calculated, for example, using the following formula (3). It can also be calculated using X-ray analysis.

[0027] Hydrate percentage (%) = {(Sample weight before melting - Sample weight after melting) ÷ 44 × (44 + 6.2 × 18)} ÷ Sample weight before melting × 100 ... (3)

[0028] The ratio (sample weight before melting - sample weight after melting) represents the weight of carbon dioxide encapsulated in the gas hydrate-containing ice. The amount of water required to encapsulate the carbon dioxide as hydrate is calculated using the theoretical hydration number of 6.2, the molecular weight of carbon dioxide of 44, and the molecular weight of water of 18 (Reference: Udachin, KA et al., (2001) “Structure, Composition, and Thermal Expansion of CO2 Hydrate from Single Crystal X-ray Diffraction Measurements”, The Journal of Physical Chemistry B, 105(19), pp. 4200-4204).

[0029] In the present invention, the gas hydrate-containing ice preferably has a gas content of 3% by weight or more. The gas content can be adjusted by conditions such as pressure, temperature, and reaction time when producing the gas hydrate-containing ice in the present invention. For example, increasing the pressure can increase the gas content of the gas hydrate-containing ice. Also, lowering the temperature increases the reaction rate and can increase the gas content of the gas hydrate-containing ice. Furthermore, if the pressure and temperature are the same, increasing the reaction time can increase the gas content of the gas hydrate-containing ice. In addition, the gas content of the gas hydrate-containing ice can be increased by dehydrating the slurry containing the gas hydrate and the unreacted solution not used in the production of the gas hydrate before freezing.

[0030] The gas content (by weight) of gas hydrate-containing ice can be calculated, for example, from the weight change when the gas hydrate-containing ice is melted at room temperature using the following formula (4).

[0031] Gas content (weight %) = (Sample weight before melting - Sample weight after melting) / Sample weight before melting × 100 ... (4)

[0032] When the gas content of the gas hydrate-containing ice is within the above range, the frozen dessert of the present invention exhibits excellent effervescence when consumed.

[0033] The frozen dessert of the present invention may be in a form in which gas hydrate-containing ice is consumed as a frozen dessert, or it may be in a form in which gas hydrate-containing ice is included in whipped cream, custard cream, fresh chocolate cream, ice cream, etc., which are consumed at freezing temperatures, and then consumed as a frozen dessert.

[0034] The gas hydrate-containing ice in the present invention preferably further satisfies the following conditions. <Condition> a) In differential scanning calorimetry (DSC), exhibiting an endothermic peak with an extrapolation start temperature of -5°C or higher. b) (Estimated average amount of solvent in the solution before gas hydrate formation) / (Estimated amount of solvent in the gas hydrate-containing ice after gas hydrate formation) > 1.2 Ice containing gas hydrate that meets all of the above conditions exhibits even greater storage stability when stored at -25°C (defrosted twice a day) for one week.

[0035] In the present invention, when the gas hydrate-containing ice is divided into multiple portions, it is preferable that the proportion of gas hydrate-containing ice that satisfies the above conditions is 50% or more of the total gas hydrate-containing ice of the multiple portions, more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and even more preferably 90% or more.

[0036] In this invention, "estimated average amount of solvent (kg) contained in the solution before gas hydrate formation" means the average mass obtained when the mass of the solvent contained in the solution for producing gas hydrate-containing ice is measured multiple times.

[0037] Furthermore, in this invention, "estimated amount of solvent (kg) contained in gas hydrate-containing ice after gas hydrate formation" means the mass of solvent obtained by subtracting the amount of water used to form the gas hydrate from the solution used to produce the gas hydrate-containing ice.

[0038] The extrapolation start temperature is preferably -4.5°C or higher, more preferably -4°C or higher, even more preferably -3.5°C or higher, even more preferably -3°C or higher, and most preferably -2.5°C or higher. The upper limit is 0°C.

[0039] In the present invention, the extrapolation start temperature at the endothermic peak of differential scanning calorimetry (DSC) of gas hydrate-containing ice can be measured by a conventional method.

[0040] The extrapolation start temperature can be adjusted depending on the type and mass of solute contained in the gas hydrate-containing ice.

[0041] For example, organic solvents contained in alcohols and fragrances have very low melting points, so when a large amount of the organic solvent is included as a solute, the extrapolation start temperature tends to be low.

[0042] Furthermore, since the number of particles increases upon dissolution of electrolytes such as sodium chloride, the extrapolation start temperature tends to be lower when the solute contains a large amount of electrolytes such as salts.

[0043] Furthermore, since substances with smaller molecular weights have a higher number of particles per unit mass than substances with larger molecular weights, the extrapolation start temperature tends to be lower when a mixture contains a large amount of substances with smaller molecular weights.

[0044] The estimated average amount of solvent contained in the solution before gas hydrate formation / estimated amount of solvent contained in the gas hydrate-containing ice after gas hydrate formation is preferably greater than 1.22, more preferably greater than 1.25, and even more preferably greater than 1.28.

[0045] The method for measuring the estimated amount of solvent contained in a solution before gas hydrate formation according to the present invention is not particularly limited, but examples include a method for measuring the amount of solvent contained in a solution for producing gas hydrate-containing ice in advance, a method for measuring the amount of solvent contained in a solution obtained by melting gas hydrate-containing ice after gas hydrate formation, and a method for determining the amount of solvent in ice with a hydrate content of 0% produced with the same amount of solvent as gas hydrate-containing ice from the following formula (5).

[0046] ΔT f =K f ·m ···(5) ΔT f :Freezing point depression degree K f : Molar freezing point depression (K·kg / mol) m: Molality (mol / kg)

[0047] In the present invention, ΔT fThe freezing point depression can be defined as the absolute value of the extrapolation start temperature in differential scanning calorimetry (DSC). In the present invention, when an aqueous solution is used as the solution, K f The molar freezing point depression is assumed to be 1.85 (K·kg / mol).

[0048] In the present invention, the amount of solvent obtained by formula (5) can be the estimated amount of solvent contained in the solution before gas hydrate formation.

[0049] The method for measuring the estimated amount of solvent contained in the gas hydrate-containing ice after gas hydrate formation according to the present invention is not particularly limited, but examples include a method of calculating from the amount of solvent contained in the solution obtained by melting the gas hydrate-containing ice after gas hydrate formation and the hydrate ratio of the gas hydrate-containing ice, a method of determining from the above formula (5), and a method of calculating by X-ray analysis.

[0050] When the "estimated average amount of solvent in the solution before gas hydrate formation / estimated amount of solvent in the gas hydrate-containing ice after gas hydrate formation," calculated using the amount of solvent measured by one of the above methods, is greater than 1.2, the gas hydrate-containing ice satisfies condition b).

[0051] The method for producing gas hydrate-containing ice according to the present invention will be described in detail below.

[0052] The present invention uses a circulating gas hydrate-containing ice production apparatus for producing gas hydrate-containing ice. A circulating gas hydrate-containing ice production apparatus is a production apparatus equipped with a mechanism that reuses a portion of the raw material solution that was not used for gas hydrate production as the raw material solution for the next gas hydrate production.

[0053] First, the raw material solution and raw material gas for generating the gas hydrate are mixed, and the raw material gas is mixed into the raw material solution (S11; gas-liquid mixing step).

[0054] Next, gas hydrate is generated from the raw material solution and the raw material gas (S12; gas hydrate generation step). Here, in the gas hydrate generation step, it is preferable to cool the mixture of the raw material solution and the raw material gas in a flowing manner, and more preferably to cool the mixture of the raw material solution and the raw material gas while flowing it in one direction. In batch-type manufacturing equipment, once hydrate formation progresses to a certain extent, the stirring stops due to the load of hydrate, and hydrate crystals grow in the absence of solution flow. As a result, the Brix value of the gas hydrate-containing ice becomes locally high, and the gas hydrate-containing ice becomes non-uniform.

[0055] Then, the gas hydrate slurry, which contains the gas hydrate and a portion of the raw material solution, and the remaining raw material solution are separated (S13; solid-liquid separation step). Here, the gas hydrate generation step and the solid-liquid separation step are performed at different locations within the manufacturing apparatus.

[0056] Finally, the gas hydrate slurry is frozen to produce gas hydrate-containing ice (S14; freezing step).

[0057] Even when steps S11 to S14 are repeated, the coefficient of variation of the Brix values ​​of the gas hydrate-containing ice of the present invention is 0.4 or less when the gas hydrate-containing ice is divided into multiple portions. The following describes a method for producing gas hydrate-containing ice by repeatedly performing steps S11 to S14.

[0058] In a method for producing gas hydrate-containing ice by repeatedly performing steps S11 to S14, the residual raw material solution can be used in the gas-liquid mixing step. In this case, the residual raw material solution is mixed with the raw material solution after the solid-liquid separation step.

[0059] Furthermore, it is preferable to separate the residual raw material solution from the residual raw material gas contained in the residual raw material solution (gas-liquid separation step). Preferably, the residual raw material solution from which the residual raw material solution and the residual raw material gas contained in the residual raw material solution have been separated is used in the gas-liquid mixing step.

[0060] Furthermore, the dehydrated solution produced by the dehydration treatment of the gas hydrate slurry can also be used in the gas-liquid mixing process.

[0061] In a method for producing gas hydrate-containing ice by repeatedly performing steps S11 to S14, it is preferable to include a concentration adjustment step for adjusting the concentration of the raw material solution, which is a mixture of the residual raw material solution and / or the dehydration treatment solution. It is possible that the raw material solution, which is a mixture of the residual raw material solution and / or the dehydration treatment solution, has a different concentration than the raw material solution used to produce the first gas hydrate-containing ice. Therefore, water is added to the raw material solution, which is a mixture of the residual raw material solution and / or the dehydration treatment solution, to adjust it to the concentration of the raw material solution used for the first generation of gas hydrate-containing ice.

[0062] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Also, the notation X~Y% in Table 1 means greater than X% and less than Y%. [Examples]

[0063] [Coefficient of variation of Brix value and storage stability of gas hydrates] <Test Example 1> Preparation of gas hydrate-containing ice according to the present invention Gas hydrate-containing ice was produced from a flavored solution and carbon dioxide using a circulating gas hydrate-containing ice production system. The flavored solution formulation is shown in Table 1 below. Specifically, a flavored solution was introduced into a circulating gas hydrate-containing ice production device, and carbon dioxide gas was supplied at a pressure of 2-3 MPa. The flavored solution and carbon dioxide were then mixed within the device. The mixture was then sent to the gas hydrate generation section of the device and cooled to the gas hydrate generation temperature while flowing in one direction. Gas hydrate was generated in this process. Using a separation mechanism within the device, the gas hydrate slurry containing the generated gas hydrate and a portion of the flavored solution was separated from the remaining flavored solution. The gas hydrate slurry was transferred to the freezing section of the apparatus and frozen at -20°C to obtain gas hydrate-containing ice. This gas hydrate-containing ice was crushed to obtain multiple samples (Example 1: Samples 1-15). In this case, the gas content of the sample was 3% by weight or more.

[0064] <Test Example 2> Production of gas hydrate-containing ice using a batch method Gas hydrate-containing ice was produced from a flavored solution and carbon dioxide using a batch-type gas hydrate-containing ice production apparatus. The flavored solution formulation is shown in Table 1 below. Specifically, carbon dioxide was blown into the flavored solution in a batch to a pressure of 3 MPa, and the hydrate formation reaction was carried out at 1°C while stirring to prepare a gas hydrate-containing solution (slurry) containing carbon dioxide hydrate and a portion of the unreacted flavored solution. This gas hydrate-containing solution (slurry) was cooled to -20°C, recovered as gas hydrate-containing ice, and crushed to obtain samples (frozen desserts) (Comparative Example 1: Samples 1-15).

[0065] The Brix values ​​and the gas hydrate retention rate (CDH retention rate) of samples 1 to 15 from Example 1 and Comparative Example 1 were measured and are shown in Table 2 below.

[0066] [Table 1]

[0067] [Table 2]

[0068] Table 1 shows that among the gas hydrate-containing ice with a coefficient of variation of Brix value of 0.417, there were many gas hydrate-containing ice with CDH retention rates in the 10% and 20% range, indicating that the storage stability of the gas hydrate was inferior to that of gas hydrate-containing ice with a coefficient of variation of Brix value of 0.110 when stored at -25°C (defrosted twice a day) for one week. Therefore, it was found that ice containing gas hydrates with a Brix coefficient of variation of 0.110 exhibits superior storage stability of the gas hydrates when stored at -25°C (defrosted twice a day) for one week.

[0069] [Storage stability of gas hydrate-containing ice that meets specific conditions] <Test Example 3> Creation of Gas Hydrate-Containing Ice First, flavored solutions were prepared according to the formulations shown in Table 3 below. Here, the solubility (mol) of each formulation is the solubility considering the ionization of the electrolyte.

[0070] [Table 3]

[0071] Gas hydrate-containing ice was prepared using flavored solutions with formulations 1 to 5. Specifically, flavored solutions 1 to 5 were each introduced into a batch-type gas hydrate-containing ice production apparatus. Carbon dioxide gas was supplied at a pressure of 2 to 3 MPa to achieve the hydrate ratios shown in Table 3, and the mixture was cooled to the gas hydrate generation temperature while being stirred. Gas hydrate was generated in this process. Subsequently, the mixture was frozen at -20°C to obtain gas hydrate-containing ice. The gas hydrate-containing ice was then crushed to obtain samples for Examples 2-10 and Comparative Examples 2-5. Here, the hydrate percentages listed in Table 3 are design values, and the actual hydrate percentage differs for each sample, as evidenced by the difference in "solvent amount (later)" between Examples 2-10 and Comparative Examples 2-5. Furthermore, the gas content of each sample was 3% by weight or more.

[0072] For each sample, the extrapolation start temperature at the endothermic peak was measured using differential scanning calorimetry (DSC). Then, using equation (5) above, the estimated average amount of solvent contained in the solution before gas hydrate formation and the estimated amount of solvent contained in the gas hydrate-containing ice after gas hydrate formation were calculated, and the ratio of (estimated average amount of solvent contained in the solution before gas hydrate formation) / (estimated amount of solvent contained in the gas hydrate-containing ice after gas hydrate formation) was determined (see "solvent ratio" in Table 4). In addition, the gas hydrate retention rate (see "retention rate" in Table 4) was measured for each sample after storage at -25°C (defrosting twice a day) for one week, and evaluated according to the following evaluation criteria.

[0073] (Evaluation Criteria) [Storage stability] ○: Gas hydrate retention rate is 50% or more △: Gas hydrate retention rate is 40% or more but less than 50% ×: Gas hydrate retention rate is less than 40%

[0074] Next, the carbonation level of each sample was evaluated. The evaluation was conducted by three experienced evaluators. If the carbonation sensation felt strongly from the gas hydrate-containing ice being evaluated, it was given a rating of ◎. If the carbonation sensation felt slightly strong in the gas hydrate-containing ice being evaluated, it was given a rating of ○. If the carbonation sensation felt weak for the gas hydrate-containing ice being evaluated, it was given a rating of △. If no carbonation sensation was felt at all with the gas hydrate-containing ice being evaluated, it was given a rating of ×.

[0075] (Evaluation Criteria) [Sensory evaluation] Ice containing gas hydrate that received a rating of ◎ from two or more evaluators received an overall rating of ◎ for its carbonation level. Ice containing gas hydrate that received a "○" rating from two or more evaluators was given an overall "○" rating for its carbonation level. Ice containing gas hydrate that received a △ rating from two or more evaluators received an overall △ rating for its carbonation level. Ice containing gas hydrate that received a "×" rating from two or more evaluators received an overall "×" rating for its carbonation level.

[0076] [Table 4]

[0077] From Example 2 and Comparative Examples 2 and 3, it was found that ice containing gas hydrate that satisfies both conditions a and b had a gas hydrate retention rate of over 50% after being stored at -25°C (defrosted twice a day) for one week, indicating excellent storage stability of the gas hydrate. Furthermore, it was found that the overall carbonation level was rated as ○ or higher.

[0078] Furthermore, from Example 2 and Comparative Examples 4-6, it was found that gas hydrate-containing ice satisfying both conditions a and b had a gas hydrate retention rate exceeding 50% after being stored at -25°C (defrosted twice a day) for one week, indicating excellent storage stability of the gas hydrate. It was also found that the overall carbonation level was rated as ○ or higher. [Industrial applicability]

[0079] According to the present invention, it is possible to provide gas hydrate-containing ice with improved hydrate stability or a frozen dessert containing the gas hydrate-containing ice.

Claims

1. Gas hydrate-containing ice in which, when the ice is divided into multiple portions, the coefficient of variation of the Brix values ​​of the multiple portions of gas hydrate-containing ice is 0.4 or less.

2. The gas hydrate-containing ice according to claim 1, wherein the gas content is 3% by weight or more.

3. Ice containing gas hydrate as described in claim 1 or 2, prepared with a flavored solution.

4. The gas hydrate-containing ice according to claim 1 or 2, which contains one or more components selected from the group consisting of flavorings, sweeteners, acidulants, salts, emulsifiers, inorganic substances, and amino acids.

5. A frozen dessert comprising gas hydrate-containing ice according to claim 1 or 2.

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