WO2018096996A1

WO2018096996A1 - Co2 hydrate for oral ingestion or complex for oral ingestion containing said co2 hydrate, and methods respectively for producing those products

Info

Publication number: WO2018096996A1
Application number: PCT/JP2017/041049
Authority: WO
Inventors: 愛辻; 紀子阿野; 雅子神辺須; 敬宏江口; 佳孝山本; 実大室町; 太郎水谷; 裕一朗山崎; 貴昭井上; 信威下條; 有希榎本
Original assignee: キリン株式会社; 国立大学法人筑波大学
Priority date: 2016-11-24
Filing date: 2017-11-15
Publication date: 2018-05-31
Also published as: JPWO2018096996A1; JP7058011B2

Abstract

The present invention addresses the problem of providing: a CO₂ hydrate for oral ingestion which is reduced in the risk of carbon dioxide intoxication when added to a food or beverage and then orally ingested through the food or beverage or orally ingested directly, and has a sufficient sensation of carbonated water and higher safety, and others; and methods for producing the CO₂ hydrate and others. The present invention also addresses the problem of providing: a CO₂ hydrate for oral ingestion, of which the sustained CO₂ release is controlled so that the maximum CO₂ generation rate upon the melting of the CO₂ hydrate under an environment similar to human oral cavity can become less than 8 mL/sec., and others; and methods for producing the CO₂ hydrate and others. The CO₂ hydrate is characterized by being so adjusted that the maximum CO₂ generation rate can become less than 8 mL/sec. (Definition of maximum CO₂ generation rate (mL/sec)) The following test is repeated three times: the CO₂ hydrate is sampled in such an amount that 0.3 to 0.36 g of CO₂ is contained in the CO₂hydrate, then the sampled CO₂ hydrate is added to 10 mL of water having a liquid temperature of 37ºC under an atmosphere having an atmospheric pressure at room temperature (37ºC) and at a humidity of 70%, then the change in weight of the solution is measured at intervals of 5 seconds for a total period of at least 30 seconds after the addition of the CO₂ hydrate to calculate the amount (mL) of CO₂ generated during every 5 seconds, and then a CO₂ generation rate (mL/sec) during every 5 seconds is calculated from the generated amount (mL). The largest value, among the values for the CO₂ generation rates (mL/sec) during every 5 seconds which are obtained by the repeated test, is employed as a maximum CO₂ generation rate (mL/sec) for the CO₂ hydrate.

Description

CO2 hydrate for oral intake or composite for oral intake containing the CO2 hydrate, and methods for producing them

The present invention relates to a CO ₂ hydrate for oral intake or a composite for oral intake containing the CO ₂ hydrate (hereinafter also referred to as “CO ₂ hydrate for oral intake, etc.”) and a method for producing them.

A substance called CO ₂ hydrate (carbon dioxide hydrate) is known. CO ₂ hydrate refers to an inclusion compound in which carbon dioxide molecules are confined in the empty space of a water molecule crystal. A water molecule forming a crystal is called a “host molecule”, and a molecule trapped in the void of the crystal of the water molecule is called a “guest molecule” or “guest substance”. Since CO ₂ hydrate decomposes into CO ₂ (carbon dioxide) and water when melted, it generates CO ₂ upon melting. CO ₂ hydrate can be produced by making CO ₂ and water into a condition of low temperature and high pressure CO ₂ partial pressure, for example, at a certain temperature and CO ₂ hydrate at that temperature. It can be manufactured under conditions including that the CO ₂ partial pressure is higher than the rate equilibrium pressure (hereinafter also referred to as “CO ₂ hydrate production conditions”). The above-mentioned conditions of “a certain temperature and the CO ₂ partial pressure higher than the equilibrium pressure of CO ₂ hydrate at that temperature” are shown in FIG. _{2 of} Non-Patent Document 1 and FIG. 7 of Non-Patent Document 2. And the equilibrium pressure curve of CO ₂ hydrate disclosed in FIG. 15 (for example, the vertical axis represents CO ₂ pressure and the horizontal axis represents temperature), the high pressure side of this curve (the equilibrium pressure curve of CO ₂ hydrate) For example, when the vertical axis represents the CO ₂ pressure and the horizontal axis represents the temperature, it is expressed as a condition of the combination of the temperature in the region (above the curve) and the CO ₂ pressure. The CO ₂ hydrate can also be produced by reacting fine ice instead of water with CO ₂ under conditions of low temperature and low pressure CO ₂ partial pressure. As the pressure of CO ₂ in the production of CO ₂ hydrate is increased, also, as the temperature of CO ₂ and water is low, CO ₂ concentration of CO ₂ hydrate tends to be higher. CO ₂ concentration of CO ₂ hydrate, depending on the preparation of CO ₂ hydrate, can be on the order of about 3-28 wt%, and the CO ₂ concentration of the carbonated water (about 0.5 wt.%) Remarkably high compared.

As an application of CO ₂ hydrate, for example, in Patent Document 1, by mixing CO ₂ hydrate with a beverage, carbonic acid is given to the beverage to produce a carbonated beverage. Patent Document 3 discloses that a carbonated supplement medium formed by covering CO ₂ hydrate with ice is added to a beverage to cool a slimmed beverage and to replenish carbon dioxide in a drained beverage. CO ₂ hydrate is mixed with frozen confectionery such as oyster ice and ice cream, so that the CO ₂ hydrate is melted in the oral cavity of the person who ate the frozen confectionery. In addition to the swooshing feeling, it is disclosed that an irritating texture can be generated such that a frozen dessert can be played in the mouth.

CO ₂ store hydrate, to transfer, from the viewpoint of suppressing such CO ₂ as possible degradation of hydrates, the temperature during storage and transport is preferably as low, CO ₂ in a lower temperature condition Higher costs are required to maintain hydrate. Therefore, at lower cost, CO ₂ from a more efficient inhibition of the decomposition of hydrate, and more effectively suppress the decomposition of CO ₂ hydrate by means other than temperature control, storage stability, storage stability Means have been developed to improve. As such means, an attempt has been made to use a phenomenon called “self-preservation effect” known in gas hydrates such as CO ₂ . The self-preserving effect of gas hydrate means that the decomposition of gas hydrate is very slow under certain specific conditions in the region of temperature and pressure conditions where gas hydrate should originally decompose relatively quickly. The effect becomes. Although the mechanism of the self-preserving effect has not yet been fully elucidated, the decomposition of the gas hydrate is an endothermic reaction, so that under certain specific conditions, the water generated on the surface due to the decomposition of the gas hydrate is once again frozen. Thus, it is considered that an ice film covers the surface of the gas hydrate, and as a result, the storage stability and storage stability of the gas hydrate are improved. In addition, the surface of gas hydrate is decomposed at atmospheric pressure below the freezing point and gas molecules are released into the gas phase, and the surface of gas hydrate is covered with an ice film. It is also thought to improve stability. For example, in Patent Document 4, gas hydrate particles in which the gas may be CO ₂ gas are placed under the decomposition conditions, and the surfaces of the particles are slightly melted to generate water. It is disclosed that the self-preserving property of the gas hydrate is enhanced by freezing the gas. In addition, Patent Document 5 improves the transportation and storage efficiency of gas hydrate by forming an ice film on the surface of the pellet in a humidified atmosphere after the step of forming a gas hydrate such as methane into a pellet. Is disclosed. Patent Document 6 discloses that after the step of forming a gas hydrate such as methane into a pellet, negatively charged raw material water is sprayed onto the pellet, and a thin and uniform water film of 10 μm to 500 μm is formed on the pellet surface. It is disclosed that a gas hydrate exhibiting sufficient self-preserving property can be produced by forming an ice and cooling it to form an ice film. However, the storage stability and storage stability related to self-storability are storage stability and storage stability at a temperature below the melting point of ice (less than about 0 ° C.). This is a concept of another dimension that is not directly related to the sustained release of carbon dioxide under conditions such as about 37 ° C.

On the other hand, as an example of adding saccharides to CO ₂ hydrate, Patent Document 7 is characterized by carbon dioxide class hydrate added with saccharides such as glucose and having foamability and sweetness when contained in the mouth. Frozen confection is disclosed, and Non-Patent Document 3 discloses that the storage stability of carbon dioxide hydrate is reduced by adding sucrose (sucrose) during the production of carbon dioxide hydrate. However, these documents is for adding sugar to water in the production of CO ₂ hydrate, for example, does not disclose coating the CO ₂ hydrate in an ice film containing saccharides.
On the other hand, as an example of adding a thickener to CO ₂ hydrate, Patent Document 8 discloses a spoon by mixing CO ₂ hydrate-containing particles with ice slurry containing stabilizers such as locust bean gum and gelatin. A method for producing ice that can be picked up is disclosed. Patent Document 9 discloses a method for producing a frozen carbonated beverage that is mixed with a frozen syrup with flavor containing a thickener such as pectin. However, these references, the CO ₂ hydrate been made to mix the frozen material containing a thickening agent, it is intended to disclose coating the CO ₂ hydrate in an ice film containing, for example, thickener Absent.

It is known that inhalation of high concentration CO ₂ gas causes carbon dioxide poisoning. Carbon dioxide poisoning can occur in several breaths, and symptoms include headache, dizziness, arrhythmia, nausea, dyspnea, and impaired consciousness. In rats, exposure to high concentrations of carbon dioxide is known to cause arrhythmia and respiratory depression. However, there are still many uncertainties regarding the conditions and mechanisms that cause human carbon dioxide poisoning. Products containing CO ₂ hydrate for oral ingestion examples inventors have been commercialized knowledge is not, the CO ₂ hydrate respect dioxide intoxication risks of oral ingestion, never been investigated.

JP 2005-224146 A Japanese Patent No. 4969683 Japanese Patent No. 4716921 Japanese Patent No. 517336 Japanese Patent No. 5153412 Japanese Patent No. 5052385 JP 2008-237034 A Japanese Patent No. 4169165 Special table 2004-512035 gazette

Under the background of the background art as described above, the present inventors have made practical use in order to carry out various studies on various uses of CO ₂ hydrate for oral intake and its practical application. Were examined in detail, especially the risk of carbon dioxide poisoning when taken orally. As a result, when 2 to 10 g of granular CO ₂ hydrate (CO ₂ content 15 to 18%) having a maximum length of 5 to 20 mm manufactured by the conventional manufacturing method is included in the oral cavity at a time, It has been found that even if the amount of CO ₂ hydrate produced by the production method is 2 g, the risk of carbon dioxide poisoning cannot be said to be sufficiently low. Thus, it has been newly found that the risk of carbon dioxide poisoning becomes a serious issue when ingesting CO ₂ hydrate into the oral cavity.
Note that the carbon dioxide intoxication risks of oral intake of the CO ₂ hydrate, in an environment similar to the human oral cavity, in the evaluation system (A) "maximum CO ₂ generation rate (mL / sec)" The objective evaluation was performed using the “maximum CO ₂ concentration in the model lung (assuming an adult) (mmHg)” in the evaluation system of (B).
The amount of CO ₂ hydrate (A) CO ₂ and contains 0.3 ~ 0.36 g, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, were added to water 10mL of liquid temperature 37 ° C., The change in weight is measured at least 30 seconds or more every 5 seconds from the addition, and the CO ₂ generation amount (mL) is calculated every 5 seconds, and the CO ₂ generation rate every 5 seconds is calculated from the generation amount (mL). The test of calculating (mL / second) was repeated three times, and the maximum value of the CO ₂ generation rate (mL / second) obtained every 5 seconds was determined as the maximum CO ₂ generation of the CO ₂ hydrate. Speed (mL / sec).
(B) a dead lung volume comprising: a model lung driven by a ventilator; an oral model; a communication pipe connecting the model lung and the oral model in communication; and a capnometer installed in the communication pipe A breathing simulator adjusted to about 200 mL was used. An outline of the breathing simulator is shown in FIG. Specifically, CO ₂ hydrate is put into the oral model, and the CO ₂ concentration (mmHg) in the exhaled gas in the communication tube when the model adult lung is driven is measured. This CO ₂ concentration (mmHg) is measured for 120 seconds or more, and the maximum value of the concentration is taken as the maximum CO ₂ concentration (mmHg) in the model lung. During the experiment, CO ₂ gas was supplied to the model lung at 200 mL / min equivalent to the amount generated in vivo.

Therefore, an object of the present invention is to solve (problem (1)) is, CO ₂ hydrate or CO ₂ hydrate composite (hereinafter represented as "CO ₂ hydrate and the like".) The edible or drinkable to Decomposition of CO ₂ hydrate etc. is progressing after adding CO ₂ hydrate etc. to cold food and drink when taking it into the mouth for the purpose of enjoying a unique texture or feeling over the throat, or a production effect that looks delicious. Yes, even when inhaling the CO ₂ gas that is being generated by the decomposition of the CO ₂ hydrate etc. at the stage of carrying it to the mouth, the risk of carbon dioxide poisoning has been reduced compared to the prior art. It is to provide a high CO ₂ hydrate for oral intake.
In addition, the problem to be solved by the present invention (problem (2)) is that, after ingesting CO ₂ hydrate or the like for the above purpose, decomposition of CO ₂ hydrate or the like in the oral environment is the problem (1). Even when a larger amount of CO ₂ gas is inhaled than in the case of the above problem (1), which is generated by proceeding more rapidly than in the case of the above, the risk of carbon dioxide poisoning is reduced more safely than before. It is to provide CO ₂ hydrate and the like for oral intake having high properties.
Furthermore, the problem to be solved by the present invention (problem (3)) is to provide a safer method for producing CO ₂ hydrate for oral intake that has a reduced risk of carbon dioxide poisoning. .
In addition, if the said subject (2) is solved, the said subject (1) will be solved naturally. This is because the decomposition rate of CO ₂ hydrate increases as the temperature increases and the risk of carbon dioxide poisoning increases, and the temperature increases or decreases depending on the temperature of the cold food or drink <temperature <oral temperature (-37 ° C). The risk of carbon dioxide poisoning due to decomposition of CO ₂ hydrate and the like when added to cold food and drink is the risk of carbon dioxide poisoning due to decomposition of CO ₂ hydrate and the like when contacted with moisture in the oral cavity. This is because it is lower than the risk.

The present inventors have made intensive studies in order to solve the above problems, the lung CO ₂ concentration is above a certain, there is a possibility that personal injury by carbon dioxide intoxication, the arterial blood carbon dioxide partial pressure 80 It is known that consciousness is confused at ~ 100mmHg (Respiratory Physiology Revised Edition for Respiratory Management) (Yodosha, Kenji Tsuji, issued December 1, 2011) ), The idea was to control the carbon dioxide partial pressure in the lungs to be less than 80 mmHg even when CO ₂ hydrate was ingested.
As a result of intensive investigation, the release of carbon dioxide in the oral cavity is slow so that the maximum CO ₂ generation rate during melting of CO ₂ hydrate in an environment similar to that in the human oral cavity is less than 8 mL / second. (Hereinafter referred to as “CO ₂ sustained-release”) can be controlled to a carbon dioxide partial pressure of less than 80 mmHg in the lung, and the carbon dioxide poisoning risk when ingesting in the oral cavity is significantly reduced and sufficient carbon dioxide is obtained. It was found that a CO ₂ hydrate for oral intake having a feeling can be obtained. In addition, the present inventors coated CO ₂ hydrate with an ice film (including an ice film containing a thickener and a sweetening component), and adjusted the thickness and composition of the ice film to be coated. It was found that the maximum CO ₂ generation rate at the time of melting of CO ₂ hydrate under an environment similar to that in the human oral cavity can be controlled. The present inventors have completed the present invention based on these findings.

Although there are prior arts (Patent Documents 4 to 6 and the like) that disclose coating CO ₂ hydrate with an ice film, these prior arts are merely self-preserving, that is, temperatures below the melting point of ice (about about This is a technique aiming to improve storage stability and storage stability at less than 0 ° C.), and at the time of melting in an environment similar to the human oral cavity (for example, 36 to 38 ° C.) as in the present invention. This is not a technique for reducing the maximum CO ₂ generation rate (improving CO ₂ sustained release). The present inventors have provided storage stability and sustained release of CO ₂ with respect to a plurality of small pellets of CO ₂ hydrate and one large block of CO ₂ hydrate containing the same amount of CO _2. In comparison, although the storage stability of the bulk CO ₂ hydrate is higher, the sustained release of CO ₂ is almost the same, or the bulk CO ₂ hydrate is rather lower (CO ₂ generation) It was confirmed that the speed was high). This indicates that the above-described improvement in storage stability is not directly related to the above-described improvement in sustained CO ₂ release.

Further, when the described relationship between the thickness of the self-preserving effect and Korimaku, for example, in [0037] of Patent Document 5, in consideration of the efficiency of transportation of CO ₂ hydrate pellets (small grain), CO ₂ hydrate pellets Therefore, it is preferable that the ice film formed on the surface of the CO ₂ hydrate pellet is desirably formed as thin as possible within a range that exhibits a self-preserving effect. Actually, in the case of an ice film for self-preserving properties as disclosed in Patent Documents 4 to 6 and the like, its thickness is at most about 500 μm or less (see, for example, Patent Document 6).

In addition, Patent Document 2 describes a carbon supplement medium formed by covering CO ₂ hydrate with ice. However, the specification discloses that CO 2 is heated at a specified pressure under a specified temperature. _A mixture of _two gases mixed in water and stirring the water to form a slurry is cooled without dehydration, and is dispersed with CO ₂ hydrate in ice. However, CO ₂ hydrate prepared in this process, not only ice, on the surface of ice is than CO ₂ hydrate is often scattered, CO ₂ sustained release of the present invention is adjusted This is different from “CO ₂ hydrate provided with an ice coating film” which is one embodiment of CO ₂ hydrate for oral intake. In fact, in the present embodiment, as a comparative example, as described in Patent Document 2, although a slurry CO ₂ hydrate is used CO ₂ hydrate cooled without dehydrating the comparative sample It was confirmed that the maximum CO ₂ generation rate is high and the risk of carbon dioxide poisoning cannot be said to be sufficiently low.

That is, the present invention
(1) CO ₂ hydrate for ingestion, wherein the maximum CO ₂ generation rate defined below is adjusted to be less than 8 mL / sec, or for ingestion containing the CO ₂ hydrate Composite:
(Definition of maximum CO ₂ generation rate (mL / sec))
0.3 was taken the amount of CO ₂ hydrate containing CO ₂ for ~ 0.36 g, The separated CO ₂ hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO ₂ every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO ₂ evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value of the CO ₂ evolution rate every 5 seconds obtained (mL / sec), The maximum CO ₂ generation rate (mL / sec) of the CO ₂ hydrate;
(2) The CO ₂ hydrate for oral consumption according to (1) above, wherein an ice coating film is provided on the CO ₂ hydrate lump so that the maximum CO ₂ generation rate is less than 8 mL / sec. Or a complex for oral consumption containing the CO ₂ hydrate,
(3) The CO ₂ hydrate for oral consumption according to (2) above, or the CO ₂ hydrate, wherein the ice coating film is an ice film having a thickness of 0.6 to 50 mm Oral ingestion compounds,
(4) CO ₂ hydrate for oral consumption according to any one of (1) to (3) above, which is CO ₂ hydrate containing 0.3 to 0.36 g CO ₂ , or A composition for oral consumption containing the CO ₂ hydrate,
(5) CO ₂ content, 3 above, wherein the ~ 28 by weight% (1) to (4) oral ingestion for CO ₂ hydrate of any one of or the CO ₂ hydrate Including ingestible composites,
(6) The ice coating film contains one or more substances selected from the group consisting of a thickener and a sweetening component, according to the above (2) to (5), CO ₂ hydrate for oral intake according to any of the above, or a composite for oral intake containing the CO ₂ hydrate,
(7) The concentration of the thickener contained in the ice coating film is 0.5% by weight or less, and / or the sweetening ingredient concentration contained in the ice coating film is 20% by weight or less. CO ₂ hydrate for oral intake according to the above (6), or a composite for oral intake containing the CO ₂ hydrate,
(8) The oral intake CO ₂ hydrate according to any one of the above (1) to (7), wherein the oral intake composite is a beverage, ice confectionery or ice cream containing an oral intake CO ₂ hydrate, Alternatively, the present invention relates to a composite for oral consumption containing the CO ₂ hydrate.

The present invention also provides:
(9) In the production of CO ₂ hydrate, maximum CO ₂ generation rate, which is defined below is characterized in that it comprises a step of adjusting to be less than 8 mL / sec, for oral ingestion CO ₂ hydrate or the Method for producing a composite for oral consumption containing CO ₂ hydrate:
(Definition of maximum CO ₂ generation rate (mL / sec))
0.3 was taken the amount of CO ₂ hydrate containing CO ₂ for ~ 0.36 g, The separated CO ₂ hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO ₂ every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO ₂ evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value of the CO ₂ evolution rate every 5 seconds obtained (mL / sec), The maximum CO ₂ generation rate (mL / sec) of the CO ₂ hydrate.

Furthermore, the present invention provides
(10) In the production of CO ₂ hydrate, maximum CO ₂ generation rate, which is defined below is characterized in that it comprises a step of adjusting to be less than 8 mL / sec, for oral ingestion CO ₂ hydrate or the Method for adjusting CO ₂ sustained release of composite for ingestion containing CO ₂ hydrate:
(Definition of maximum CO ₂ generation rate (mL / sec))
0.3 was taken the amount of CO ₂ hydrate containing CO ₂ for ~ 0.36 g, The separated CO ₂ hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO ₂ every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO ₂ evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value among the CO ₂ evolution rate every 5 seconds obtained (mL / sec), The maximum CO ₂ generation rate (mL / sec) of the CO ₂ hydrate.

According to the present invention, a more safe CO for ingestion having sufficient carbon dioxide feeling while reducing the risk of carbon dioxide poisoning when ingested after being added to food or drink or when directly ingested. ₂ hydrates and the like, and methods for producing them, and in particular, CO ₂ such that the maximum CO ₂ generation rate upon melting in an environment similar to that in the human oral cavity is less than 8 mL / _second. It is possible to provide an oral intake CO ₂ hydrate with controlled release properties, an oral intake composite containing the CO ₂ hydrate, a production method thereof, and the like.

It is a figure which shows the outline | summary of the respiration simulator used in the Example. The measurement item is end expiratory CO ₂ partial pressure. The CO ₂ cylinder supplies CO ₂ gas equivalent to the amount of CO ₂ production at the time of adult rest (200 mL / min), and the ventilator drives the model lung at the set ventilation.

The present invention, the maximum CO ₂ (herein, simply "maximum CO ₂ evolution rate" also displays.) Generation rate adjusted so that less than 8 mL / sec by oral ingestion for CO ₂ as defined below Hydrate or a complex for oral intake containing the CO ₂ hydrate (hereinafter also referred to as “CO ₂ hydrate for oral intake of the present invention”) and a production method thereof (hereinafter “the present invention”) It is also indicated as “Manufacturing method”.
(Definition of maximum CO ₂ generation rate (mL / sec))
0.3 was taken the amount of CO ₂ hydrate containing CO ₂ for ~ 0.36 g, The separated CO ₂ hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO ₂ every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO ₂ evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value of the CO ₂ evolution rate every 5 seconds obtained (mL / sec), The maximum CO ₂ generation rate (mL / second) such as the CO ₂ hydrate is set.

The CO ₂ hydrate for oral intake of the present invention is adjusted so that the maximum CO ₂ generation rate is less than 8 mL / second, that is, the CO ₂ sustained release property is adjusted. The CO ₂ hydrate for oral consumption of the present invention that is adjusted so that the maximum CO ₂ generation rate is less than 8 mL / second is a highly safe CO ₂ hydrate for oral intake of carbon dioxide poisoning. Also, means in the present specification, "CO ₂ hydrate having sufficient carbon feeling", the maximum CO ₂ evolution rate is 1 mL / sec or more, the CO ₂ hydrate is more preferably 1.5 mL / sec or more To do.

Further, the present invention is the manufacturing of CO ₂ hydrate, maximum CO ₂ generation rate 8 mL / oral intake for CO ₂ hydrate and the like, characterized in that adjusted to be less than a second CO ₂ sustained release (Hereinafter also referred to as “the CO ₂ sustained release adjusting method of the present invention”).

In the present invention, “CO ₂ hydrate (carbon dioxide hydrate)” means a solid inclusion compound in which carbon dioxide molecules are confined in the empty space of a crystal of water molecules. CO ₂ hydrate is usually an icy crystal, and releases carbon dioxide while melting, for example, under standard atmospheric pressure conditions and under temperature conditions where ice melts.

1. <CO ₂ hydrate for oral intake of the present invention>
The oral intake for CO ₂ hydrate of the present invention, the maximum CO ₂ generation rate, a CO ₂ hydrate orally ingested, which is adjusted to be less than 8 mL / sec. The oral intake CO ₂ hydrate of the present invention is not particularly limited as long as it is such oral intake CO ₂ hydrate, such as shape, size, CO ₂ content, and production method. The composite for oral consumption of the present invention means a substance for oral intake including the CO ₂ hydrate for oral intake of the present invention. The composition for oral intake of the present invention is not particularly limited in terms of composition, shape, size, CO ₂ content, production method, etc. as long as it is a substance for oral intake including the CO ₂ hydrate for oral intake of the present invention. Not. Examples of the substance for oral intake other than the CO ₂ hydrate for oral intake of the present invention in the composite for oral intake of the present invention include foods and drinks such as frozen confectionery (for example, ice), confectionery, food, and beverage. Beverages and frozen desserts are preferred, among which beverages, ice desserts (eg ice) and ice creams are more preferred, among which ice desserts (eg ice) and ice creams are more preferred. In addition, as a form of such food or drink, it is preferable that the food or drink (preferably ice) is frozen by coating the oral ingestion CO ₂ hydrate in a film form.

The maximum CO ₂ generation rate of the CO ₂ hydrate for oral intake of the present invention is not particularly limited as long as it is less than 8 mL / second, and those skilled in the art will feel carbonation in the flavor design of the product to be used for such CO ₂ hydrate. In accordance with the above, a suitable maximum CO ₂ generation rate can be set as appropriate. From the viewpoint of the balance between reducing the risk of carbon dioxide poisoning when ingested in the mouth and obtaining a sufficient carbonic sensation, the upper limit of the maximum CO ₂ generation rate is 7.5 mL / second or less, 7 mL / second or less, Examples include 6 mL / second or less, 5 mL / second or less, and the lower limit includes 1 mL / second or more, 1.5 mL / second or more, 2 mL / second or more, 2.5 mL / second or more, 3 mL / second or more. The numerical ranges of all combinations represented by any numerical value listed as the lower limit and any numerical value listed as the upper limit are disclosed herein, but preferred numerical ranges are 1-8 mL / second, 1 5 to 7.5 mL / second, 2 to 8 mL / second, 2 to 7.5 mL / second, and the like. It should be noted that the maximum CO ₂ generation rate of the oral intake composite of the present invention is usually slower than the maximum CO ₂ generation rate of the oral intake CO ₂ hydrate of the present invention contained in the composite. This is because the substance includes the CO ₂ hydrate for oral intake of the present invention, and the substance other than the CO ₂ hydrate in the composite usually has a lower CO ₂ concentration than the CO ₂ hydrate.

As the above-mentioned CO ₂ hydrate for ingestion adjusted so that the maximum CO ₂ generation rate is less than 8 mL / second, an ice coating film is provided on the CO ₂ hydrate lump (that is, the CO ₂ is formed on the ice film). ₂ hydrate the coated), CO ₂ and hydrate the maximum CO ₂ generation rate is adjusted to be less than 8 mL / sec, by adjusting the CO ₂ content, the maximum CO ₂ evolution rate is 8 mL / CO ₂ hydrate adjusted to be less than 1 second, and the like. Among them, from the viewpoint of obtaining a more sufficient carbon dioxide feeling while significantly reducing the risk of carbon dioxide poisoning when ingested in the oral cavity, CO ₂ hydrate by providing the coating film of ice (to cover the CO ₂ hydrate in an ice film) mass is adjusted CO ₂ hydrate as the maximum CO ₂ generation rate is less than 8 mL / sec And the like to apply. By providing an ice coating film on the CO ₂ hydrate lump, as a CO ₂ hydrate for oral intake adjusted so that the maximum CO ₂ generation rate is less than 8 mL / second, specifically, a thickness of 0 Preferred examples include CO ₂ hydrate coated with an ice film of .6 to 50 mm (hereinafter also referred to as “ice film coated CO ₂ hydrate”).

The shape of the CO ₂ hydrate for oral intake of the present invention can be appropriately set according to the product design of the product to be used for the CO ₂ hydrate for oral intake of the present invention. Body shapes; substantially polyhedron shapes such as a substantially rectangular parallelepiped shape; or shapes having irregularities in these shapes; and crushing in various shapes obtained by appropriately crushing a CO ₂ hydrate lump. A piece (lump) may be sufficient. The shape of the composite for oral consumption of the present invention can be appropriately set according to the type, composition, etc. of the composite. For example, when the composite is an individual as a whole, the shape of the composite Examples thereof include a substantially spherical shape, a substantially ellipsoidal shape, a substantially polyhedral shape such as a substantially rectangular parallelepiped shape, or a shape further provided with irregularities in these shapes.

The size of the CO ₂ hydrate for oral intake of the present invention can be appropriately set according to the product design of the product to be used for the CO ₂ hydrate for oral intake of the present invention. Examples of the maximum length of ₂ hydrates include 1 to 100 mm, 2 to 50 mm, 3 to 30 mm, 4 to 25 mm, and 5 to 20 mm. In the present specification, "the maximum length of the CO ₂ hydrate for oral ingestion" are tied two points of the surface of the mass of CO ₂ hydrate orally ingested, and, among the line segments passing through the center of gravity of the mass, It means the length of the longest line segment. In addition, the size of the composite for oral intake of the present invention can be appropriately set according to the product design of the product to be used of the composite, for example, when the composite is an individual as a whole Examples of the size of the composite include 1 to 200 mm, 3 to 100 mm, 5 to 80 mm, 7 to 50 mm, and 7 to 25 mm as the maximum length of CO ₂ hydrate for oral intake.

The carbon dioxide content (CO ₂ content) of the CO ₂ hydrate for oral intake of the present invention is not particularly limited as long as the maximum CO ₂ generation rate is less than 8 mL / second, and CO ₂ for oral intake of the present invention. Although it can set suitably according to the product design etc. of the product for which hydrate is used, when the CO ₂ hydrate for oral consumption of the present invention is ice film-coated CO ₂ hydrate, the lower limit of the CO ₂ content rate For example, 3% by weight or more, preferably 5% by weight or more, more preferably 7% by weight or more, further preferably 10% by weight or more, more preferably 12% by weight or more. Examples of the upper limit of the CO ₂ content include 28 weight% or less, 23 weight% or less, 18 weight% or less is mentioned. Incidentally, herein interchangeably, CO ₂ content of the case of the ice film covering CO ₂ hydrate, the ratio of the weight of CO ₂ relative to the total weight of the ice film covering CO ₂ hydrate containing ice film (%) To do. On the other hand, the CO ₂ hydrate for ingestion of the present invention was not ice film-coated CO ₂ hydrate, but was adjusted so that the maximum CO ₂ generation rate was less than 8 mL / second by adjusting the CO ₂ content. In the case of CO ₂ hydrate, the lower limit of the CO ₂ content is, for example, 1% by weight or more, preferably 2.5% by weight or more, more preferably 4% by weight or more, and the upper limit of the CO ₂ content is, for example, Examples include 10% by weight or less, 8% by weight or less, and 6% by weight or less.

The carbon dioxide content (CO ₂ content) of the composite for oral intake of the present invention is not particularly limited, and is appropriately set according to the product design of the product to be used for the CO ₂ hydrate for oral intake of the present invention. However, the lower limit of the CO ₂ content is, for example, 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 7% by weight or more, more preferably 9% by weight or more. Examples of the upper limit of the CO ₂ content include 25% by weight or less, 20% by weight or less, and 15% by weight or less. In the present specification, the CO ₂ content of the oral intake composite of the present invention means the ratio (%) of the weight of CO _{2 to} the total weight of the oral intake composite of the present invention.

The CO ₂ content in the CO ₂ hydrate for oral intake of the present invention is determined by “the level of CO ₂ partial pressure”, “degree of dehydration treatment”, “consolidation” when producing the CO ₂ hydrate for oral intake of the present invention. It can be adjusted according to “whether or not to perform the molding process”, “the level of compaction pressure when the compacting process is performed”, “the thickness of the ice film”, and the like. For example, when making CO ₂ hydrate, “increase the CO ₂ partial pressure”, “increase the degree of dehydration”, “perform compaction processing”, “increase the compaction pressure when performing compaction processing “Yes,” the CO ₂ content of the CO ₂ hydrate can be increased. Incidentally, when the CO ₂ hydrate melts, the CO ₂ CO ₂ contained in the hydrate is released, so that amount of the weight is decreased, CO ₂ content of CO ₂ hydrate for oral ingestion, for example, From the change in weight when the CO ₂ hydrate for oral intake is melted at room temperature, it can be calculated using the following formula.
(CO ₂ content) = (sample weight before melting−sample weight after melting) / sample weight before melting)

CO ₂ content in the oral ingestion composite of the present invention, and CO ₂ content in the oral ingestion for CO ₂ hydrate of the present invention to be contained in the oral ingestion for composites, is contained in the oral ingestion for composites it can be adjusted by the mixing ratio or the like of the CO ₂ hydrate orally ingested. CO ₂ content in the oral ingestion composite of the present invention can be calculated by the same method as CO ₂ content of CO ₂ hydrate orally ingested.

The CO ₂ hydrate for oral intake of the present invention has a “low temperature condition”, “high pressure condition”, or “low temperature condition” for distribution and storage from the viewpoint of keeping it more stable for a longer period of time. It is preferable to hold | maintain under "under high pressure conditions." Among these, from the viewpoint of simplicity of holding, it is preferable to hold under “low temperature conditions”, and it is more preferable to hold under normal pressure and “low temperature conditions”.

The upper limit temperature in the above “low temperature condition” is preferably 0 ° C. or less, more preferably −5 ° C. or less, further preferably −10 ° C. or less, more preferably −15 ° C. or less, still more preferably −20 ° C., More preferred is −25 ° C., and the lower limit temperature in the “low temperature condition” is −273 ° C. or higher, −80 ° C. or higher, −50 ° C. or higher, −40 ° C. or higher, −30 ° C. or higher, etc. It is done.

Examples of the lower limit pressure under the “high pressure condition” include 1050 hectopascals (hPa) or higher, preferably 1150 hPa or higher, more preferably 1300 hPa or higher, and even more preferably 1500 hPa or higher. As 15,000 hPa or less, 12000 hPa or less, 10000 hPa or less, 8000 hPa or less, 5000 hPa or less, etc. are mentioned. In addition, all the pressures described in this paragraph are expressed as absolute pressures.

(Ice film coated CO ₂ hydrate)
As described above, the CO ₂ hydrate for oral consumption of the present invention preferably includes the ice film-coated CO ₂ hydrate of the present invention, and the oral film of the present invention includes the ice film of the present invention. A composite for oral intake containing coated CO ₂ hydrate is preferred. Such an ice film-coated CO ₂ hydrate is not particularly limited as long as it is a CO ₂ hydrate coated with an ice film having a thickness of 0.6 to 50 mm, such as shape, size, CO ₂ content, and production method.

(Ice film)
The thickness of the ice film in the present invention is not particularly limited as long as it is 0.6 to 50 mm, but preferably 0.6 to 30 mm, more preferably 0.6 to 20 mm, still more preferably 0.7 to 5 mm, More preferred is 0.7 to 4 mm, and still more preferred is 0.8 to 3.5 mm.

The “ice film thickness” in the present specification means an average value of the ice film thickness covering the CO ₂ hydrate, and the “ice film thickness” includes, for example, the ice film coating. The average value of the thickness of the ice film at 3 to 10 (preferably 5) positions selected at random in the CO ₂ hydrate ice film is included. The ice film thickness at a position where the ice film coating CO ₂ hydrate is present means the thickness of the ice film in the direction perpendicular to the plane when the surface of the ice film at the position is a plane. When is a curved surface, it means the thickness of the ice film perpendicular to the tangential plane of the ice film surface at that position. Further, when one ice film-covered CO ₂ hydrate includes _two or more CO ₂ hydrate lumps, the boundary surfaces of the ice films of the CO ₂ hydrate lumps are adjacent to each other. A perpendicular bisector that is a line segment connecting points on each surface of each CO ₂ hydrate lump and having the shortest length is preferable.

The thickness of the ice film may be different depending on the position of the surface of the ice film covering CO ₂ hydrate, but preferably is substantially uniform across the surface of the ice film covering CO ₂ hydrate, the CO ₂ hydrate The ratio of the “thickness of the ice film at the thickest position” to the “thickness of the ice film at the thinnest position” is, for example, higher than 1.0 and lower than or equal to 5.0, preferably 1.0 to 4.0, more preferably Is preferably 1.0 to 3.0.

The "ice film covering CO ₂ hydrate" as used herein, unless the maximum CO ₂ generation rate is adjusted to less than 8 mL / sec, at least a portion of the surface is not covered with ice film CO ₂ hydrate Is included for convenience, but it is preferable that the entire surface is covered with an ice film. More specifically, for "total surface area of the ice film covering CO ₂ hydrate", "in an ice film covering CO ₂ hydrate, the surface area of a portion glacial film" ratio of (%) is preferably 70 % Or more, more preferably 80% or more, further preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, more preferably 97% or more, still more preferably 98% or more, more preferably 99%. As mentioned above, it is preferable that it is most preferably 100%.

In addition, one ice film-coated CO ₂ hydrate may contain one CO ₂ hydrate chunk, or two or more CO ₂ hydrate chunks, It preferably contains one CO ₂ hydrate mass. One ice film covering CO ₂ hydrate, the number of two or if it contains 3 or more CO ₂ hydrate mass, CO ₂ hydrate mass contained in one of the ice film covering CO ₂ hydrate On the other hand, the CO ₂ hydrate mass of 60% or more as a proportion may be an ice film-coated CO ₂ hydrate, preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. More preferably, it is preferable that the number of CO ₂ hydrate blocks in a ratio of 95% or more, most preferably 100%, is ice film-coated CO ₂ hydrate.

The ice film in the present invention is an ice film, and as such ice, it may be composed only of ice or may contain an arbitrary substance other than ice. Such optional substances include one or more substances selected from the group consisting of thickeners, sweetening ingredients, emulsifiers and oils and fats, among which are selected from the group consisting of thickeners and sweetening ingredients. 1 type or 2 or more types of substances are preferably mentioned, and 1 type or 2 or more types of thickeners are more preferable, and 1 type or 2 or more types of thickeners containing at least xanthan gum are more preferable. Can be mentioned. As described above, the ice film in the present invention includes a film formed by freezing food and drink such as frozen confectionery (for example, ice), confectionery, food, and beverage.

The above thickener means a substance that can improve the viscosity of food and drink by adding it to food and drink. Such thickener includes xanthan gum, carrageenan, guar gum, tamarind gum, gellan gum, locust. Bean gum, tara gum, carboxymethylcellulose, pectin, pullulan, propylene glycol, gelatin, gum arabic, diytan gum, starch, dextrin, alginic acid, locust bean gum, etc., among which xanthan gum, pectin, guar gum, carrageenan, carboxymethylcellulose , Locust bean gum and the like are preferable, among which xanthan gum, pectin, and locust bean gum are more preferable. One thickener may be used, or two or more thickeners may be used in combination.

When the ice film in the present invention contains a thickener, the concentration of the thickener in the ice film is appropriately set according to the flavor design of the product to be used for the CO ₂ hydrate for oral intake of the present invention. For example, it is higher than 0% by weight and lower than 5% by weight, preferably 0.01 to 4.5% by weight, more preferably 0.01 to 4.0% by weight, and still more preferably 0.05 to 0%. 0.6% by weight, more preferably 0.05 to 0.5% by weight, and still more preferably 0.1 to 0.5% by weight.

The above-mentioned “sweet ingredient” refers to an ingredient exhibiting sweetness, such as brown sugar, white sugar, cassonade (red sugar), Wasanbon, sorghum sugar, maple sugar and other sugar-containing sugars. , Refined sugars such as salmon sugar (white disaccharide, medium disaccharide, granulated sugar, etc.), car sugar (super white sugar, tri-sugar etc.), processed sugar (corn sugar, ice sugar, powdered sugar, granulated sugar etc.), liquid sugar etc. , Monosaccharides (glucose, fructose, wood sugar, sorbose, galactose, isomerized sugar, etc.), disaccharides (sucrose cake, maltose, lactose, isomerized lactose, palatinose, etc.), oligosaccharides (fructooligosaccharides, maltooligosaccharides, isomaltoligosaccharides) , Galactooligosaccharides, coupling sugar, etc.), sugar alcohols (erythritol, sorbitol, xylitol, mannitol, maltitol, isomaltitol, lactitol) In addition to saccharide sweeteners such as maltotriitol, isomaltoriitol, panitol, oligosaccharide alcohol, powdered reduced maltose starch syrup, etc., natural non-sugar sweeteners (stevia extract, licorice extract, etc.) Sweeteners such as high-intensity sweeteners such as sugar sweeteners (aspartame, acesulfame K, etc.) can be mentioned. One sweetening component may be used, or two or more sweetening components may be used in combination.

When the ice membrane in the present invention contains a sweetening component, the total concentration of the sweetening components in the ice membrane should be appropriately set according to the flavor design of the product to be used for the oral ingestion CO ₂ hydrate. For example, it is higher than 0% by weight and not more than 30% by weight, preferably 1 to 25% by weight.

The above-mentioned emulsifier refers to a substance having an emulsifying action, and as such an emulsifier, those that can be used for food can be widely adopted, for example, fatty acid monoglyceride, fatty acid diglyceride, fatty acid triglyceride, propylene glycol fatty acid ester, Sucrose fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, lecithin, quillaja saponin, yucca saponin, soybean saponin, modified starch (acid-degraded starch, oxidized starch, pregelatinized starch, grafted starch, carboxymethyl group, hydroxyalkyl group And the like, esterified starch obtained by reacting acetic acid, phosphoric acid and the like, crosslinked starch in which a polyfunctional group is bonded between hydroxyl groups of two or more starches, wet heat-treated starch, and the like. One type of emulsifier may be used, or two or more types may be used in combination.

When the ice film in the present invention contains an emulsifier, the concentration of the emulsifier in the ice film can be appropriately set according to the flavor design of the product to be used for the ingestible CO ₂ hydrate of the present invention. For example, it is higher than 0% by weight and not more than 0.5% by weight, preferably 0.001 to 0.5% by weight, more preferably 0.01 to 0.4% by weight, still more preferably 0.01 to 0.3%. % By weight.

The above fats and oils refer to esters of glycerin and fatty acids, and as such fats and oils, those that can be used for food can be widely adopted, for example, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil , Rice bran oil, corn oil, safflower oil, olive oil, kapok oil, sesame oil, evening primrose oil, palm oil, shea fat, monkey fat, cacao butter, palm oil, palm kernel oil and other vegetable oils; Animal fats such as pork fat, fish oil, whale oil, and the like, and further, fats and oils alone or in combination, or processed fats and oils subjected to curing, fractionation, transesterification and the like thereof. 1 type may be used for fats and oils, and 2 or more types may be used together.

When the ice film in the present invention contains fats and oils, the concentration of the fats and oils in the ice film can be appropriately set according to the flavor design of the product to be used for the oral ingestion CO ₂ hydrate. For example, it is higher than 0 wt% and 40 wt% or less, preferably 0.01 to 35 wt%, more preferably 0.1 to 30 wt%, still more preferably 0.1 to 25 wt%, more preferably 0. 1 to 20% by weight, more preferably 0.1 to 18% by weight.

The concentration of an arbitrary component in the ice film in the present invention is measured by, for example, melting only the ice film and then applying a known method such as HPLC method, GC-MS method, LC-MS method to the solution. can do.

The ice film in the present invention may contain other components in addition to or without the above optional components. Other components include pigments and fragrances.

In addition, when the CO ₂ hydrate for oral intake of the present invention is used as a frozen confectionery such as ice confectionery or ice cream as described later, an ice film may be formed with a raw material mixture of ice confectionery or ice cream as described later. .

(Method of coating CO ₂ hydrate with ice film)
The method for coating the CO ₂ hydrate with an ice film (that is, the method of providing an ice coating film on the CO ₂ hydrate block) is not particularly limited as long as the CO ₂ hydrate can be coated with the ice film. , for example, a thin ice prepared in accordance with the surface shape of the CO ₂ hydrate (including ice containing optional component), CO ₂ may be a method of pasting on the surface of the hydrate, but the CO ₂ hydrate Since the surface of the CO ₂ hydrate is brought into contact with “water” or “an aqueous solution or suspension containing an optional component” in that it can be more easily coated with an ice film having a more uniform thickness, A method of freezing the “aqueous solution or suspension containing an arbitrary component” is preferably mentioned. As a method for bringing the surface of CO ₂ hydrate into contact with “water” or “an aqueous solution or suspension containing an optional component”, for example, (i) CO ₂ hydrate is converted into “water” or “an aqueous solution or suspension containing an optional component”. A method of immersing in a turbid liquid, (ii) a method of applying “water” or “an aqueous solution or suspension containing an optional component” to the surface of CO ₂ hydrate, or (iii) “water” or “optional component” Or a method of spraying the surface of the CO ₂ hydrate by spraying or atomizing the aqueous solution or suspension containing the liquid to the surface of the CO ₂ hydrate, or (iv) “water” or “an aqueous solution or suspension containing an optional component” "a method in which contact with the surface of the CO ₂ hydrate in the vaporized or atomized by ultrasonic vibrations and the like. Among these, from the viewpoint that can be coated with uniform ice film from the thickness of the CO ₂ hydrate, Method (iii) above and method (iv) Is preferred.

A method of freezing the “water” or “aqueous solution or suspension containing an optional component” after bringing the surface of the CO ₂ hydrate into contact with “water” or “an aqueous solution or suspension containing the optional component” as is not particularly limited, and the CO ₂ hydrate "water" or "aqueous solution or suspension containing the optional component" is in contact with the surface it may be cooled with liquid nitrogen or the like, in advance of CO ₂ hydrate It may be sufficiently cooled so that “water” or “an aqueous solution or suspension containing an optional component” in contact with the surface is frozen.

Further, after bringing the surface of the CO ₂ hydrate into contact with “water” or “an aqueous solution or suspension containing an optional component”, the “water” or “aqueous solution or suspension containing an optional component” is frozen. In this method, the contact and the number of times of freezing the ice film before adjusting the ice film to a desired thickness are such that the maximum CO ₂ generation rate of the obtained ice film-coated CO ₂ hydrate is less than 8 mL / second. As long as there is no particular limitation, it may be once or twice or more. Further, the upper limit of the number of treatments cannot be generally specified because it depends on the target ice film thickness, the method of coating the ice film, etc., but it is 20 times or less, 15 times or less, 10 times or less, or 8 times or less. Can be mentioned.

The thickness of the ice film can be adjusted by the amount of “water” or “aqueous solution or suspension containing an optional component” to be brought into contact with the surface of the CO ₂ hydrate, the number of times of contact, and the like.

The liquid temperature of “water” or “aqueous solution or suspension containing optional components” when the surface of CO ₂ hydrate is brought into contact with “water” or “aqueous solution or suspension containing optional components” is particularly limited. However, it is possible to form an ice film having a more uniform thickness, avoid melting of CO ₂ hydrate by the temperature of “water” or “aqueous solution or suspension containing an optional component”, etc. From the viewpoint, −5 to 15 ° C. is preferable, 0 to 10 ° C. is more preferable, and 1 to 8 ° C. is further preferable.

(Ice film covering CO ₂ hydrate fabrication CO ₂ hydrate)
The maximum CO ₂ generation rate of the CO ₂ hydrate used for the production of the ice film-coated CO ₂ hydrate of the present invention (hereinafter also simply referred to as “CO ₂ hydrate for ice film coating”) is 8 mL / second or more. From the viewpoint of obtaining a CO ₂ hydrate for oral intake that has a more sufficient carbonic sensation, the maximum CO ₂ generation rate of the CO ₂ hydrate for ice film coating is preferably 8 mL / second or more, more preferably It is 10 mL / second or more, preferably 15 mL / second or less, more preferably 13 mL / second or less.

The shape, size, CO ₂ content, production method, etc. of the CO ₂ hydrate for ice film coating are not particularly limited. The shape and size of the CO ₂ hydrate for ice film coating are the shape and size obtained by removing the ice film in the CO ₂ hydrate for oral intake of the present invention. The size of the CO ₂ hydrate for ice film coating can be appropriately set according to the flavor design of the product to be used for the CO ₂ hydrate for oral intake of the present invention. For example, CO ₂ for ice film coating Examples of the maximum hydrate length include 0.5 to 30 mm, 1 to 25 mm, and 2 to 20 mm.

The CO ₂ content of the CO ₂ hydrate for ice film coating is not particularly limited as long as the maximum CO ₂ generation rate is less than 8 mL / second when the CO ₂ hydrate for oral intake of the present invention is used. Although it can be set as appropriate according to the product design of the target product of CO ₂ hydrate for ingestion of the oral cavity, the lower limit of the CO ₂ content is, for example, 3% by weight or more, preferably 6% by weight or more, more preferably Is 8% by weight or more, more preferably 11% by weight or more, and more preferably 13% by weight or more. Examples of the upper limit of the CO ₂ content include 28% by weight or less and 25% by weight or less.

The method for producing CO ₂ hydrate for ice film coating is not particularly limited as long as CO ₂ hydrate can be produced, and the raw water is stirred while blowing CO ₂ into the raw water under conditions that satisfy the CO ₂ hydrate production conditions. Ordinary methods such as a gas-liquid stirring method or a water spray method in which raw water is sprayed into CO ₂ under conditions satisfying CO ₂ hydrate production conditions can be used. Since the CO ₂ hydrate produced by these methods is usually in the form of a slurry in which fine particles of CO ₂ hydrate are mixed with unreacted water, dehydration is performed to increase the concentration of CO ₂ hydrate. It is preferable to carry out the treatment. CO ₂ hydrate having a relatively low water content by dehydration (ie, a relatively high concentration of CO ₂ hydrate) can be compression-molded into a certain shape (for example, a spherical shape or a rectangular parallelepiped shape) by a pellet molding machine. preferable. The compression-molded CO ₂ hydrate may be used in the present invention as it is, or may be further crushed as necessary. As described above, as a method for producing the CO ₂ hydrate for ice film coating, the method using raw water is relatively widely used, but fine ice (raw material ice) is used instead of water (raw water). ) and the CO _2, a low temperature, and can be used how disulfide under the conditions of low pressure CO ₂ partial pressure for producing a CO ₂ hydrate.

As described above, the “CO ₂ hydrate production condition” is a condition in which the CO ₂ partial pressure (CO ₂ pressure) is higher than the equilibrium pressure of CO ₂ hydrate at that temperature. The above “conditions in which the partial pressure of CO ₂ is higher than the equilibrium pressure of CO ₂ hydrate” are shown in FIG. 2 of Non-Patent Document 1 (J. Chem. Eng. Data (1991) 36, 68-71) Equilibrium pressure curve of CO ₂ hydrate disclosed in FIG. 7 and FIG. 15 of Patent Document 2 (J. Chem. Eng. Data (2008), 53, 2182-2188) (for example, the vertical axis represents CO ₂ pressure) , The horizontal axis represents temperature), the region on the high pressure side of this curve (in the equilibrium pressure curve of CO ₂ hydrate, for example, the vertical axis represents CO ₂ pressure, and the horizontal axis represents temperature, above the curve) It is expressed as a condition of a combination of CO ₂ pressure and temperature. Specific examples of the CO ₂ hydrate generation conditions include a combination condition of “within a range of −20 to 4 ° C.” and “within a range of carbon dioxide pressure of 1.8 to 4 MPa”, and a range of “−20 to −4 ° C.” The combination of “inside” and “within carbon dioxide pressure in the range of 1.3 to 1.8 MPa” can be mentioned.

The CO ₂ hydrate for coating an ice film may be a CO ₂ hydrate composed of only carbon dioxide and ice (hereinafter also referred to as “CO ₂ hydrate containing no optional components and other components”). You may contain the 1 type (s) or 2 or more types of substance selected from the group which consists of a thickener, a sweetening component, an emulsifier, fats and oils, a pigment | dye, and a fragrance | flavor. Examples of the “pigment” include carotenoid pigments such as marigold pigments, flavonoid pigments such as safflower pigments, anthocyanin pigments, gardenia pigments, betanin pigments such as beet pigments, chlorella, chlorophyll, etc. However, it is not particularly limited to these.

The CO ₂ hydrate for oral intake of the present invention may be accommodated in the packaging container or may not be accommodated. As such a packaging container, for example, a packaging container having the same shape and material as those usually used for beverage ice or the like can be used. Examples of such packaging containers include resin bags such as polyethylene resins and resin cups.

(Use of CO ₂ hydrate for oral intake of the present invention, composite for oral intake of the present invention)
The CO ₂ hydrate for buccal intake of the present invention can be suitably used as a CO ₂ hydrate for buccal intake because the sustained release of CO ₂ is adjusted. The CO ₂ hydrate for oral consumption of the present invention may be used as it is as a frozen confectionery or ice confectionery, or may be added to a substance for oral consumption such as other frozen confectionery, confectionery, food, beverages and the like as follows: The composition for oral intake of the present invention may be prepared by mixing, mixing, or sprinkling.

The oral intake composite of the present invention is a substance for oral intake including (including) the oral intake CO ₂ hydrate of the present invention. As the oral intake composite, the oral intake CO of the present invention is included. containing ₂ hydrate, frozen desserts (e.g. ice), confectionery, food and beverages products such as beverages, and among them, a beverage containing an oral intake for CO ₂ hydrate of the present invention, frozen desserts (e.g., ice) are preferably mentioned Among these, beverages, ice confections (for example, ice), and ice creams containing the CO ₂ hydrate for oral intake of the present invention are more preferable, and ice confections (for example, ice) containing the CO ₂ hydrate for oral intake of the present invention are more preferable. ) And ice cream are more preferable. Incidentally, a preferred embodiment from another aspect of the oral ingestion composite of the present invention, one or more of the ice film covering CO ₂ substances for oral ingestion comprising a hydrate of the present invention (preferably ices (e.g. Ice) and ice creams). Among them, the individual “ice film-coated CO ₂ hydrates of the present invention” contained in such oral intake substances (preferably ice confectionery (eg ice), ice creams) are included. More preferably mentioned are substances for oral intake (preferably ice confectionery (for example, ice), ice creams) each containing one CO ₂ hydrate mass.

The CO ₂ hydrate for oral intake of the present invention makes a crackling sound when it melts, and the CO ₂ gas pops out, so that a visual effect and an auditory effect can be obtained, and it is stimulating that a frozen confection can be played in the oral cavity. A good texture can be obtained. In addition, the oral ingestion composite (preferably ice confectionery, ice cream) of the present invention has a remarkable carbonic acid sensation possessed by the CO ₂ hydrate for oral intake of the present invention, and other foods and beverages (preferably ice confectionery, ice cream). Class) Unprecedented texture and flavor can be brought together with the original flavor and texture.

Examples of the frozen dessert include ice creams, ice confections, etc., and such ice creams include ice cream, ice milk, lacto ice, etc., and the above ice desserts include popsicles, sleet, shaved ice, ice, Examples include sherbet, frozen yogurt and shake. As confectionery and food, jelly, pudding, yogurt, nata de coco, agar, apricot tofu, tapioca, syrup, bee, fresh cream, millefeuille, marshmallow, fruit, chocolate, cheese, cookies, wafer, cake, tart, pie, cream puff, Examples include moose, bavaroa, panna cotta, donut, waffle, baumkuchen, castella, kudari mochi, yokan, white ball, shiruko, zenzai, warabimochi, rice ball, and kinako.

</ RTI> Examples of the beverage include alcoholic beverages and non-alcoholic beverages. Examples of such alcoholic beverages include sparkling liquors such as beer, sparkling liquor, and other sparkling liquors; Japanese sake; fruit liquors; distilled liquors; liqueurs; Examples of the Japanese sake include Daiginjo sake, Junmai Daiginjo sake, Ginjo sake, Junmai Ginjo sake, Honjozo sake, Junmai sake and the like. Examples of the fruit liquor include wine (fruit wine) such as grape wine (grape), apple wine (cider), and sweet fruit liquor such as sherry and port, among which wine is preferred. Among these, grape wine is more preferable, and white wine and rose wine are more preferable. Examples of the distilled liquor include shochu, whiskey, vodka and spirits. Examples of the liqueur include plum wine, cassis liqueur, orange liqueur, lemon liqueur, grapefruit liqueur, lime liqueur, apricot liqueur, strawberry liqueur, yogurt liqueur and the like.

Non-alcoholic beverages include water such as mineral water; carbonated beverages such as cola, ginger ale and cider; beer-taste beverages; fruit juice-containing beverages; vegetable juice-containing beverages; sports beverages; isotonic beverages; , Green tea, oolong tea, barley tea, shachu tea, etc .; cocoa drink; jelly drink; milk such as milk, low-fat milk, processed milk; milk drink; dairy drink; lactic acid bacteria drink; soy milk; Beauty drink agent; salmon and the like.

The oral ingestion composite of the present invention is a normal oral ingestion substance (preferably a food or drink, more preferably a beverage, ice confectionery (for example, ice cream) except that it contains the oral ingestion CO ₂ hydrate of the present invention. ), Ice cream, more preferably ice confectionery (eg ice), ice cream).

In the composite for oral intake of the present invention, the aspect of containing the CO ₂ hydrate for oral intake of the present invention is not particularly limited, and for example, the CO ₂ hydride for oral intake of the present invention on a substance for oral intake. The aspect in which the rate is carried may be sufficient, and the aspect in which a part or all of the CO ₂ hydrate for oral intake of the present invention is embedded in the substance for oral intake may be used. In addition, for the sake of convenience, the oral container containing the oral intake CO ₂ hydrate of the present invention is also included in the packaging container in which the oral intake substance and the oral intake CO ₂ hydrate of the present invention are separately included. Included in “substances for use”.

The content of the CO ₂ hydrate for oral intake of the present invention in the composite for oral intake of the present invention is not particularly limited, but is the total amount of the composite for oral intake of the present invention including the CO ₂ hydrate for oral intake of the present invention. 3 wt% or more, 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, and the upper limit is, for example, 100 wt% or less, 90 wt% or less, 80 wt% or less. Can be mentioned.

The method for producing the oral ingestion composite of the present invention is a method for making the oral ingestion CO ₂ hydrate included in the oral ingestion substance in the usual method for producing an oral ingestion composite. As long as it is not particularly limited, for example, in a normal production method of a substance for oral intake such as food and drink, in a normal production method of the substance for oral intake, The method of adding and mixing the hydrate for oral intake of the invention is preferably mentioned.

In more detail about the manufacturing method in case the compound for oral intake of this invention is ice confectionery or ice cream, in the normal manufacturing method of ice confectionery or ice cream, the raw material mixture of ice confectionery or ice cream is cooled. The method of adding and mixing the hydrate for oral intake of the present invention is preferably mentioned. The above ice confectionery materials vary depending on the type of ice confectionery, but include sweetening ingredients; emulsifiers; stabilizers; fragrances; pigments, etc. The above ice cream materials may also depend on the type of ice cream. Although different, for example, proteins such as skim milk powder and skim milk; edible fats and oils such as vegetable oils and milk fats; sweetening ingredients; emulsifiers; stabilizers; fragrances;

The above-mentioned ice creams may not be filled in corn, waffle dough, etc., but may be filled.

The oral ingestion composite of the present invention may or may not be accommodated in a packaging container. As such a packaging container, a packaging container having the same shape and material as those normally used for the substance for oral intake can be used.

2. <Production method of the present invention>
The method for producing CO ₂ hydrate for oral intake of the present invention (production method of the present invention) includes adjusting the maximum CO ₂ generation rate to be less than 8 mL / sec in the production of CO ₂ hydrate. As long as it is, there is no particular limitation.

As a method of maximum CO ₂ generation rate described above is adjusted to be less than 8 mL / sec is not particularly limited, the coating providing a coating of ice on the CO ₂ hydrate mass the (CO ₂ hydrate in an ice film to) by, and how the maximum CO ₂ generation rate is adjusted to be less than 8 mL / sec, by adjusting the CO ₂ content of CO ₂ hydrate, maximum CO ₂ generation rate and less than 8 mL / sec In particular, from the viewpoint of obtaining a more sufficient carbon dioxide sensation while significantly reducing the risk of carbon dioxide poisoning when ingested in the mouth, an ice coating film is formed on the CO ₂ hydrate mass. A method of adjusting the maximum CO ₂ generation rate to be less than 8 mL / second is preferable by providing a CO ₂ hydrate, and the CO ₂ hydrate is covered with an ice film having a thickness of 0.6 to 50 mm. Thus, a method of adjusting the maximum CO ₂ generation rate to be less than 8 mL / second is more preferable.

Korimaku and, a method of coating a CO ₂ hydrate in an ice layer, the ice film covering CO ₂ hydrate and the like are as described above.

3. <CO ₂ sustained release adjusting method of the present invention>
CO ₂ sustained release method of adjusting CO ₂ hydrate and the like of the present invention (CO ₂ sustained release adjusting method of the present invention), in the production of CO ₂ hydrate, maximum CO ₂ generation rate is less than 8 mL / sec As long as it includes adjustment, there is no particular limitation.

As a method of maximum CO ₂ evolution rate of the above CO ₂ hydrate is adjusted to be less than 8 mL / sec is not particularly limited, provided the coating film of ice CO ₂ hydrate masses (CO ₂ hydrate by the coating with ice film), a method of maximum CO ₂ generation rate is adjusted to be less than 8 mL / sec, by adjusting the CO ₂ content of CO ₂ hydrate, maximum CO ₂ evolution rate The method of adjusting so that it may become less than 8 mL / second etc. is mentioned, Especially, from a viewpoint of obtaining more sufficient carbonic acid feeling from the viewpoint of obtaining carbon dioxide poisoning remarkably at the time of ingestion in an oral cavity, it is a CO ₂ hydrate lump. by providing the coating film of ice (CO ₂ hydrate the coated ice film), a method of maximum CO ₂ generation rate is adjusted to be less than 8 mL / sec are preferably mentioned By coating the CO ₂ hydrate in an ice layer having a thickness of 0.6 ~ 50 mm, methods maximum CO ₂ generation rate is adjusted to be less than 8 mL / sec can be given more preferably.

4). <Flavor improving agent of the present invention>
The flavor improving agent of the present invention is not particularly limited as long as it contains the CO ₂ hydrate for oral intake of the present invention. The CO ₂ hydrate for oral intake of the present invention is as described above. The flavor improving agent of the present invention can enhance the carbon dioxide feeling sufficient for food and drink while reducing the risk of carbon dioxide poisoning. That is, the flavor improving agent of the present invention can give a more sufficient carbonic sense to food and drink more safely.

The flavor improving agent of this invention can be used by making it contain in food-drinks. The amount of the flavor improving agent of the present invention can be appropriately set according to the in flavor improving agent and concentration of the oral intake for CO ₂ hydrate and the like of the present invention, the degree of carbonate feeling like which enhance the food products .

The concentration of the flavor improving agent of the present invention, such as CO ₂ hydrate for oral intake of the present invention, can be appropriately set according to the flavor design of the target product of the flavor improving agent of the present invention. 0.1 to 100% by weight, preferably 1 to 95% by weight, more preferably 5 to 90% by weight.

The flavor improving agent of the present invention may consist only of the CO ₂ hydrate for oral intake of the present invention or the like, or may contain optional components other than the CO ₂ hydrate for oral intake of the present invention. . Such optional substances include thickeners, extenders and the like.

The flavor improving agent of the present invention can be produced, for example, by mixing an optional component with the CO ₂ hydrate for oral intake of the present invention. The flavor improving agent of this invention may be accommodated in the packaging container, and does not need to be accommodated. As such a packaging container, for example, a packaging container having the same shape and material as those usually used for beverage ice or the like can be used. Examples of such packaging containers include resin bags such as polyethylene resins and resin cups.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

<Method>
[1] CO ₂ hydrate preparation prior literature (Japanese Patent No. 3090687, JP-T 2004-512035, Patent No. 4,969,683) to the reference, was generated in the CO ₂ hydrate. Specifically, CO ₂ gas was blown into 4 L of water so as to be 3 MPa, and the hydrate formation reaction was allowed to proceed at 1 ° C. while stirring to prepare a sherbet-like slurry containing CO ₂ hydrate. This sherbet-like slurry was cooled to −20 ° C., recovered as CO ₂ hydrate, and prepared to be 0.4 to 0.6 g per grain on liquid nitrogen. The CO ₂ content of these CO ₂ hydrates was 15 to 18%.

[2] Coating of CO ₂ hydrate with ice film [2-1] Preparation of solution used for coating Xanthan gum (manufactured by Saneigen Co., Ltd., Vistop D-3000-ES), pectin (manufactured by Sanki Co., Ltd., VIS -J-TF), carrageenan (manufactured by CP Kelco, CSM-2) or granulated sugar was dissolved in ion-exchanged water at room temperature to prepare a viscous solution having a viscosity of 1 mPas to 7500 mPas. The viscosity was measured using a B-type viscometer (LVDV-II + Pro, manufactured by Brookfield) at a liquid temperature of 5 ° C. The viscosity was measured based on JIS Z8803. The produced viscous solution was stored at 5 ° C. and used for the coating treatment of CO ₂ hydrate described later. In addition, ion-exchanged water was also stored at 5 ° C. and used for the coating treatment of CO ₂ hydrate described later.

[2-2] Coating of CO ₂ hydrate with ice film 2.0 g of granular CO ₂ hydrate produced by the method of [1] above is cooled and taken out in liquid nitrogen. Coat the surface of CO ₂ hydrate with an ice film of viscous solution or an ion-exchanged water film by immersing in the prepared viscous solution or ion-exchanged water at 5 ° C and then immediately cooling in liquid nitrogen. did. This coating operation was repeated until the ice film of the viscous solution or the ice film of ion-exchanged water had a predetermined thickness on the CO ₂ hydrate surface to obtain a CO ₂ hydrate sample for oral intake. The obtained CO ₂ hydrate sample for ingestion was entirely covered with an ice film. The thickness of the ice film was calculated based on the weight of the viscous solution or ion-exchanged water used for coating, assuming that one granular CO ₂ hydrate used was a sphere having a diameter of 0.50 cm. For example, if the ion-exchanged water and granulated CO ₂ hydrate 2.0g was 3.0g coatings for granular CO ₂ hydrate is 4 tablets, one particle per ion exchange water is 0.75g coated It will be a thing. If the specific gravity of ice is 0.92 and the volume of 0.75 g of ion-exchanged water is calculated and the surface of a sphere having a diameter of 0.50 cm is uniformly coated, the diameter of the CO ₂ hydrate grains increases by 0.18 cm. It will be done. This increased thickness for 0.18 cm was taken as an estimate of the ice film thickness.

[3] CO ₂ hydrate samples up CO ₂ generation rate measurement test each CO ₂ hydrate sample from the liquid nitrogen 10-15 minutes before being subjected to testing, and transferred to -20 ° C. conditions. Each CO ₂ hydrate sample was confirmed to have a surface temperature of −20 ° C. or higher by thermography (manufactured by FLIR, E40sc) before being subjected to the experiment.

As a measuring instrument, a precision balance was installed in an incubator with a temperature of 37 ° C. and a humidity of 70%. A stainless steel container (diameter: 110 mm, depth: 50 mm) containing 200 mL of water at a liquid temperature of 37 ° C. is placed on the weighing pan in the hood of the precision balance, and 10 mL of water at a liquid temperature of 37 ° C. is placed on the bottom of the stainless steel container. Was placed (50 mL capacity, diameter 45 mm, depth 75 mm).

Each CO ₂ hydrate sample was added to the water in the beaker, and the change in weight was measured every 5 seconds for 10 minutes after the addition. When the CO ₂ hydrate is melted, the CO ₂ gas contained in the CO ₂ hydrate is released, and the corresponding weight is reduced. From the weight change, the CO ₂ generation amount (mL) every 5 seconds was calculated. The measurement test of calculating the CO ₂ generation rate (mL / second) every 5 seconds from the CO ₂ generation amount (mL) was repeated three times for each CO ₂ hydrate sample. The maximum value of the CO ₂ generation rate (mL / second) every 5 seconds obtained by repeating the measurement test three times was defined as the maximum CO ₂ generation rate (mL / second) of the CO ₂ hydrate sample.

[4] Model lung maximum CO ₂ concentration measurement test using a respiratory simulator A model (respiratory simulator: Fig. 1) simulating the airway system including the lungs of an adult was prepared, and the sample and ventilation conditions were changed. The degree of increase in pulmonary CO ₂ concentration was examined using ₂ partial pressure as an index.
Each CO ₂ hydrate sample was transferred from above liquid nitrogen to −20 ° C. conditions 10-15 minutes prior to testing. One model lung (Michigan Instruments, TTL model lung) was ventilated with a ventilator (COVIDIEN, Ventilator 840), and the other model lung was physically driven to simulate spontaneous breathing. . An oro-nasal cavity / laryopharynx (hereinafter referred to as “oral cavity”) model was connected to the model lung, and a capnometer (Ventrac, manufactured by NOVAMETRIX) was installed at the site corresponding to the larynx. The oral cavity model is assumed to be an adult, and the physiological dead space (region in which no gas is exchanged with blood in the respiratory system) is set to 193 mL. The scanning model the lung CO ₂ production level during adult resting was flowed at a constant 200 mL / min of CO ₂ gas.

Each CO ₂ hydrate sample was put into the above breathing simulator oral model, and 5 mL of 37 ° C. water was injected into the oral model one minute after the input. The CO ₂ concentration (mmHg) in the exhaled gas is measured every 10 seconds from the time of water injection with the above-mentioned capnometer, and the average of the measured CO ₂ concentration every 30 seconds from the start of measurement is the maximum CO ₂ concentration in the model lung (mmHg). ). About each CO2 hydrate sample, the tidal volume of the driving side ventilator was changed to 400 mL, 600 mL, and 800 mL, and the measurement was performed.

<Result>
[5] the presence or absence of ice film in CO ₂ hydrate surface, thickness, presence or absence of ice film in effect CO ₂ hydrate surface providing the sustained release of CO ₂ gas in the CO ₂ hydrate, thickness, CO ₂ In order to investigate the effect of hydrate on the sustained release of CO ₂ gas, the measurement test of the maximum CO ₂ generation rate in [3] above for the samples of Examples 1 to 3 and Comparative Example 1 below, and The measurement test of the maximum CO ₂ concentration in the model lung of the above [4] was conducted.

[5-1] Examples 1 to 3
0.1% of xanthan gum and 20% of granulated sugar with respect to 2.0 g of granular CO ₂ hydrate (CO ₂ content 16.8%; CO ₂ content 0.34 g) produced by the method of [1] above. % Viscous solution 5.0 to 6.0 g, or 3.0 to 4.0 g, or 1.0 to 2.0 g with a viscosity of 26.4 mPas (liquid temperature 6.1 ° C., rotation speed 50 rpm). And CO ₂ hydrate samples for oral consumption that were coated by the method of [2] above were designated as Example 1, Example 2, and Example 3, respectively. The thicknesses of the ice films covering the CO ₂ hydrate samples for oral intake of Examples 1 to 3 are 2.5 to 3.1 mm, 1.6 to 2.2 mm, and 0.8 to 1.3 mm, respectively. Met.

[5-2] Comparative Example 1
The granular CO ₂ hydrate 2.0 g (CO ₂ content 17.5%; CO ₂ content 0.35 g) produced by the method [1] was used as the CO ₂ hydrate sample of Comparative Example 1.

[5-3] Maximum CO ₂ generation rate, and, for each model intrapulmonary maximum CO ₂ concentration in Comparative Example 1 of CO ₂ hydrate samples and Examples 1 to 3 for oral ingestion CO ₂ hydrate samples, the [ The maximum CO ₂ generation rate (mL / second) was measured by the method [3], and the maximum CO ₂ concentration (mmHg) in the model lung was measured by the method [4]. These results are shown in Table 1.

As shown in the results of Table 1, in the sample of Comparative Example 1 in which CO ₂ hydrate was used as it was and no ice coating film was provided, the maximum CO ₂ generation rate was 10 mL / second or more, and the model The maximum CO ₂ concentration in the lung exceeded 80 mmHg. A CO ₂ concentration in the lung of more than 80 mmHg is a concentration at which there is a high possibility of danger to the human body due to carbon dioxide poisoning. Meanwhile, as shown in the results of Table 1, CO ₂ in the hydrate ice coating film provided CO ₂ hydrate maximum CO ₂ evolution rate of about 8 mL / sec less than the described embodiments 1-3 Sample The maximum CO ₂ concentration in the model lung was maintained below 70 mmHg. Further, as compared with the sample of Example 3, since the lower the maximum CO ₂ evolution rate of samples of Examples 1 and 2, by increasing the ice film, maximum CO ₂ generation rate reduction of CO ₂ hydrate It was shown that CO ₂ generation from CO ₂ hydrate becomes more gradual. That is, as the ice layer of CO ₂ hydrate is thick, sustained release CO ₂ that is higher CO ₂ hydrate was shown. The ease of onset of carbon dioxide poisoning is affected by individual differences such as age, weight, and the presence or absence of specific diseases, so it is difficult to specify the concentration at which there is a risk of carbon dioxide poisoning. However, this experiment provided useful findings for ensuring safety when the sample was included in the oral cavity.

[6] Examination of composition of ice film covering CO ₂ hydrate In order to examine the composition of ice film exhibiting higher CO ₂ sustained release property, the following CO ₂ hydride for oral intake of Examples 4 to 7 For the rate sample, the measurement test for the maximum CO ₂ generation rate in [3] and the measurement test for the maximum CO ₂ concentration in the model lung in [4] were performed.

[6-1] Examples 4 to 7
Xanthan gum was 0%, 0.01%, and 0.002% with respect to 2.0 g of granular CO ₂ hydrate produced by the method of [1] (CO ₂ content: 16.0%; CO ₂ content: 0.32 g). Each of the CO ₂ hydrate samples for oral consumption coated with the method of [2] above using 3.0 to 4.0 g of viscous solutions dissolved to 1% or 0.5%, respectively. 4, Example 5 and Example 6.

[6-2] Maximum CO ₂ generation rate and model lung maximum CO ₂ concentration For each oral ingestion CO ₂ hydrate sample of Examples 4 to 6, the maximum CO ₂ generation rate ( mL / second) and the maximum CO ₂ concentration (mmHg) in the model lung was measured by the method of [4] above. Moreover, the viscosity of each viscous solution used for the coating of CO ₂ hydrate was measured at 5 ° C. These results are shown in Table 2. The type of spindle used for measuring the viscosity is “SC4-18” for any of the examples, the angular velocity is 20.94 rad / s for the samples of Examples 4 and 5, and Example 6 is used. In the case of this sample, it was set to 0.63 rad / s.

As shown in the results of Table 2, the samples of Example 5 and Example 6 have a lower maximum CO ₂ generation rate (mL / second) compared to the sample of Example 4, and the sample of Example 5 Compared to the sample of Example 6, the maximum CO ₂ evolution rate (mL / sec) was even lower. From the results in Table 2, it was shown that the maximum CO ₂ generation rate from the hydrate can be further reduced by adjusting the viscosity of the viscous solution used for the production of the coating ice film. From the results shown in Table 2, the concentration of xanthan gum is preferably 0.01 to 0.7% by weight, more preferably 0.01 to 0.6% by weight, still more preferably 0.05 to 0.6% by weight. %, More preferably 0.05 to 0.5% by weight, still more preferably 0.1 to 0.5% by weight.

According to the present invention, when it is taken into the mouth after being added to a food or drink, or when it is taken directly into the mouth, the risk of carbon dioxide poisoning is reduced, while having a sufficient carbonation sensation, for safer mouth intake. CO ₂ hydrate, or a composite containing the oral ingested CO ₂ hydrate, can be provided and is a unique texture to eat, or a pleasant throat feel to drink, or a CO ₂ hydrate that looks even more delicious You can enjoy production effects.

Claims

A CO 2 hydrate for oral consumption, or a complex for oral consumption containing the CO 2 hydrate, wherein the maximum CO 2 generation rate defined below is adjusted to be less than 8 mL / second.
(Definition of maximum CO 2 generation rate (mL / sec))
0.3 was taken the amount of CO 2 hydrate containing CO 2 for ~ 0.36 g, The separated CO 2 hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO 2 every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO 2 evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value of the CO 2 evolution rate every 5 seconds obtained (mL / sec), The maximum CO 2 generation rate (mL / second) of the CO 2 hydrate is used.
The CO 2 hydrate for oral consumption according to claim 1, wherein an ice coating film is provided on the CO 2 hydrate lump so that the maximum CO 2 generation rate is less than 8 mL / sec, or A composite for oral consumption comprising CO 2 hydrate.
3. The oral ingestion CO 2 hydrate according to claim 2 or the oral ingestion composite comprising the CO 2 hydrate according to claim 2, wherein the ice coating film is an ice film having a thickness of 0.6 to 50 mm. object.
0.3 to claims 1 to 3 either oral ingestion for CO 2 hydrate according to, which is a CO 2 hydrate containing CO 2 of 0.36 g, or the CO 2 hydrate Containing for oral consumption.
CO 2 content, 3, characterized in that to 28 by weight% claims 1 to 4 or oral ingestion for CO 2 hydrate according to or the CO oral ingestion composite containing 2 hydrate, .
The oral cavity according to any one of claims 2 to 5, wherein the ice coating film contains one or more substances selected from the group consisting of a thickener and a sweetening ingredient. CO 2 hydrate for ingestion, or a composition for oral intake containing the CO 2 hydrate.
The concentration of the thickener contained in the ice coating film is 0.5% by weight or less, and / or the sweetness component concentration contained in the ice coating film is 20% by weight or less. The oral intake CO 2 hydrate according to claim 6 or a composite for oral intake containing the CO 2 hydrate.
Oral intake for composites, beverage containing CO 2 hydrate orally ingested edible ice or ice cream in a claims 1 to 7, or oral ingestion for CO 2 hydrate according to or the CO 2 hydrate, A composite for oral consumption comprising:
In the production of CO 2 hydrate, the method includes a step of adjusting the maximum CO 2 generation rate defined below to be less than 8 mL / second, or a CO 2 hydrate for oral consumption or the CO 2 hydrate A method for producing a composite for oral consumption comprising a rate.
(Definition of maximum CO 2 generation rate (mL / sec))
0.3 was taken the amount of CO 2 hydrate containing CO 2 for ~ 0.36 g, The separated CO 2 hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO 2 every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO 2 evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value of the CO 2 evolution rate every 5 seconds obtained (mL / sec), The maximum CO 2 generation rate (mL / second) of the CO 2 hydrate is used.
In the production of CO 2 hydrate, the method includes a step of adjusting the maximum CO 2 generation rate defined below to be less than 8 mL / second, or a CO 2 hydrate for oral consumption or the CO 2 hydrate The method for adjusting CO 2 sustained release of a composite for oral consumption containing a rate.
(Definition of maximum CO 2 generation rate (mL / sec))
0.3 was taken the amount of CO 2 hydrate containing CO 2 for ~ 0.36 g, The separated CO 2 hydrate, in an atmosphere of atmospheric pressure at room temperature 37 ° C., 70% humidity, the liquid temperature Add to 10 mL of water at 37 ° C., measure the change in weight at least 30 seconds or more every 5 seconds from the addition, calculate the generation amount (mL) of CO 2 every 5 seconds, and calculate the generation amount (mL the test that calculates respective CO 2 evolution rate every 5 seconds (mL / sec) from), repeated three times, the maximum value of the CO 2 evolution rate every 5 seconds obtained (mL / sec), The maximum CO 2 generation rate (mL / second) of the CO 2 hydrate is used.