JP4729649B1 - Hydrogen gas-containing calcium carbonate and method for producing the same - Google Patents
Hydrogen gas-containing calcium carbonate and method for producing the same Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 202
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011049 pearl Substances 0.000 claims abstract description 12
- 150000002016 disaccharides Chemical class 0.000 claims abstract description 6
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 18
- 239000004071 soot Substances 0.000 claims description 8
- 241000904011 Carcharhinus perezii Species 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 235000015872 dietary supplement Nutrition 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000011148 porous material Substances 0.000 description 16
- 230000000717 retained effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 108010006161 conchiolin Proteins 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 6
- 241000237502 Ostreidae Species 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000020636 oyster Nutrition 0.000 description 5
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- -1 hydrogen compound Chemical class 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 241000237503 Pectinidae Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 235000014510 cooky Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007902 hard capsule Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 208000028867 ischemia Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000010410 reperfusion Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
【課題】
１ｇあたりに、２５℃において０．１〜５０μＬの水素ガスが保持されて成り、温度２５℃、湿度５０％、大気圧下の開放状態において、水素ガス保持量が製造後から半減するまでに要する期間が６ヶ月以上である水素ガス含有炭酸カルシウム及びその製造方法を提供する。
【解決手段】
［ａ］成分：貝殻、真珠、風化造礁珊瑚、炭酸カルシウムから成る群より選択される１種又は２種以上の粒子、を
［ｂ］成分：メタノール、エタノール、プロパノール、単糖類水溶液、二糖類水溶液、有機酸水溶液から成る群より選択される１種又は２種以上、
に浸漬して、１０〜６０ｋＨｚの超音波を１〜６０分間照射することにより、［ｂ］成分を［ａ］成分に付着させ、これを風乾後、２５０〜５００℃で１０分間〜５時間焼成することにより、水素源物質を熱分解させて水素ガスを発生させ、水素ガスを保持する［ａ］成分の粒子を得る。
【選択図】なし【Task】
Per gram, 0.1 to 50 μL of hydrogen gas is held at 25 ° C., and it is required for the hydrogen gas holding amount to be halved after production in an open state at a temperature of 25 ° C., a humidity of 50% and atmospheric pressure. A hydrogen gas-containing calcium carbonate having a period of 6 months or more and a method for producing the same are provided.
[Solution]
[A] component: one or more kinds of particles selected from the group consisting of shells, pearls, weathered reef lees and calcium carbonate, [b] component: methanol, ethanol, propanol, monosaccharide aqueous solution, disaccharide One or more selected from the group consisting of an aqueous solution and an organic acid aqueous solution,
The [b] component is attached to the [a] component by irradiating with 10 to 60 kHz ultrasonic waves for 1 to 60 minutes, air-dried, and then fired at 250 to 500 ° C. for 10 minutes to 5 hours. By doing so, the hydrogen source material is thermally decomposed to generate hydrogen gas, and [a] component particles that hold the hydrogen gas are obtained.
[Selection figure] None
Description
本発明は、水素ガスを含有した炭酸カルシウム及びその製造方法に関する。より詳しくは、水素ガスの保持量が経時で減少し難い水素ガス含有炭酸カルシウム及びその製造方法に関する。 The present invention relates to calcium carbonate containing hydrogen gas and a method for producing the same. More specifically, the present invention relates to a hydrogen gas-containing calcium carbonate in which the amount of hydrogen gas retained is less likely to decrease with time and a method for producing the same.
水素ガスを体内に取り入れ、生体に対して有害なフリーラジカルと水素ガスとを反応させて疾病の改善をはかろうとする試みがなされている。水素ガスはフリーラジカルであるヒドロキシラジカルと反応して、生体に対して無害な水を生成することは良く知られている。以下の式（１）で示すように、ヒドロキシラジカルは水素原子が持つプロトンと電子を供与されて水となり無毒化される。 Attempts have been made to improve disease by taking hydrogen gas into the body and reacting hydrogen gas with free radicals harmful to the living body. It is well known that hydrogen gas reacts with hydroxy radicals, which are free radicals, to produce water that is harmless to the living body. As shown in the following formula (1), the hydroxyl radical is detoxified as water by being supplied with protons and electrons of the hydrogen atom.
水素ガスを血中に導入する場合、水素ガスは脳まで到達し、脳内の虚血・再灌流時の活性酸素による様々な弊害を改善することが知られている。しかし、活性酸素と反応するまでの間に、水素ガスが消失ないし大部分が消費されてしまう場合がある。そのため、上記弊害を改善することが困難となる場合もある。また、水素ガスをそのまま血中に取り入れる方法は、ドラッグデリバリという観点からは必ずしも理想的な方法とはいえない。 When hydrogen gas is introduced into the blood, it is known that the hydrogen gas reaches the brain and improves various adverse effects caused by active oxygen during ischemia / reperfusion in the brain. However, there is a case where hydrogen gas disappears or is mostly consumed before reacting with active oxygen. For this reason, it may be difficult to improve the above adverse effects. Further, the method of taking hydrogen gas into the blood as it is is not necessarily an ideal method from the viewpoint of drug delivery.
また、水素ガスを日常的に簡単に摂取するという観点から、水素ガスが溶解している水を飲用することが考えられる。しかし、水素ガスの水に対する溶解度は低い。２５℃、１気圧の条件において、水素ガスは水に対して１．５５（ｍｇ／Ｌ）しか溶解しない。さらに、水素ガスの水に対する溶解量は、ヘンリーの法則に従い、気相中の水素ガスの分圧に比例する。そのため、水素ガスの分圧が小さい場合、即ち気相中に水素ガスが殆ど存在しない場合（例えば、大気中）は、水中に水素ガスを溶解させても、水素ガスは短時間のうちに蒸発逸散される。そのため、水素ガスは水中に長く滞留させることができない。従って、実質的に必要な量の水素ガスを、水中に一定の期間溶存させることはできない。 From the viewpoint of easily taking hydrogen gas on a daily basis, it is conceivable to drink water in which hydrogen gas is dissolved. However, the solubility of hydrogen gas in water is low. Under conditions of 25 ° C. and 1 atm, hydrogen gas dissolves only 1.55 (mg / L) in water. Furthermore, the amount of hydrogen gas dissolved in water is proportional to the partial pressure of hydrogen gas in the gas phase in accordance with Henry's law. Therefore, when the partial pressure of hydrogen gas is small, that is, when there is almost no hydrogen gas in the gas phase (for example, in the atmosphere), even if hydrogen gas is dissolved in water, the hydrogen gas evaporates within a short time. Dissipated. Therefore, hydrogen gas cannot stay for a long time in water. Therefore, a substantially necessary amount of hydrogen gas cannot be dissolved in water for a certain period.
特許文献１には、珊瑚、牡蠣殻を原料として製造する粉末状の担体に、水素ガスを保持させる方法が記載されている。珊瑚や牡蠣殻は、これらの成長生育過程において、骨格をなす炭酸カルシウムの層間に、コンキオリンを含む蛋白質などの有機物が不可避的に蓄積されている。そのため、珊瑚や牡蠣殻を還元的雰囲気下で焼成すると、この有機物の熱分解生成物である水素ガスが生じる。この水素ガスは、炭酸カルシウムの細孔内に含有される。この炭酸カルシウムに保持される水素ガスは、拡散消失され易い。 Patent Document 1 describes a method in which hydrogen gas is held on a powdery carrier that is produced using straw and oyster shells as raw materials. In these growth and growth processes, cocoons and oyster shells inevitably accumulate organic substances such as proteins containing conchiolin between the layers of calcium carbonate forming the skeleton. Therefore, when firewood or oyster shells are fired in a reducing atmosphere, hydrogen gas, which is a thermal decomposition product of the organic matter, is generated. This hydrogen gas is contained in the pores of calcium carbonate. The hydrogen gas held in this calcium carbonate is easily diffused and lost.
本発明の課題は、製品の品質を一定に保ち、かつ水素ガス保持量が長期に亘って減少しない水素ガス含有炭酸カルシウム及びその製造方法を提供することにある。 An object of the present invention is to provide a hydrogen gas-containing calcium carbonate in which the product quality is kept constant and the hydrogen gas retention amount does not decrease over a long period of time, and a method for producing the same.
本発明者は、炭酸カルシウム等の担体に、水素化合物を付着させて焼成することにより、水素ガス保持量が一定の水素ガス含有炭酸カルシウムが得られることを見出し、特許出願を行った（特願２００９−０４００９３、特許文献２）。これらの発明において、担体に水素化合物を付着させ、更に超音波を照射することにより、水素化合物を担体の微細な細孔の深部にまで含浸させることができることを見出した。そして、この担体を焼成して得られる水素ガス含有炭酸カルシウムは、開放した大気中で保存する場合、水素ガス保持量が経時で殆ど低下しないことを見出し、本発明を完成するに至った。 The present inventor found that hydrogen gas-containing calcium carbonate having a constant hydrogen gas retention amount can be obtained by attaching a hydrogen compound to a carrier such as calcium carbonate and firing, and filed a patent application (Japanese Patent Application). 2009-040093, Patent Document 2). In these inventions, it has been found that the hydrogen compound can be impregnated into the deep pores of the carrier by attaching the hydrogen compound to the carrier and further irradiating with ultrasonic waves. The hydrogen gas-containing calcium carbonate obtained by calcining this support has been found to show that the amount of hydrogen gas retained hardly decreases with time when stored in an open atmosphere, and the present invention has been completed.
上記課題を解決する本発明は以下に記載するものである。 The present invention for solving the above problems is described below.
〔１〕
下記の［ａ］成分、
［ａ］成分：貝殻、真珠、風化造礁珊瑚、炭酸カルシウムから成る群より選択される１種又は２種以上の粒子
と、
前記［ａ］成分の粒子内に保持される水素ガスと、から成る水素ガス含有炭酸カルシウムであって、
前記［ａ］成分１ｇあたりに、２５℃において０．１〜５０μＬの水素ガスが保持されて成り、
温度２５℃、湿度５０％、大気圧下の開放状態において製造後６ヶ月間保存した後の水素ガス残存量が５０％以上であることを特徴とする水素ガス含有炭酸カルシウム。
[1]
The following [a] component,
[A] component: 1 type or 2 or more types of particle | grains selected from the group which consists of a shell, a pearl, a weathered reef shark, a calcium carbonate,
A hydrogen gas-containing calcium carbonate comprising hydrogen gas held in the particles of the component [a],
0.1 g to 50 μL of hydrogen gas is held at 25 ° C. per 1 g of the component [a],
A hydrogen gas-containing calcium carbonate characterized by having a hydrogen gas residual amount of 50% or more after storage for 6 months after production in an open state at a temperature of 25 ° C., a humidity of 50%, and atmospheric pressure.
以下の〔２〕〜〔６〕に記載の発明も本発明に含まれる。 The inventions described in [2] to [6] below are also included in the present invention.
〔２〕
［ａ］成分の平均粒子径が１〜１００μｍである〔１〕に記載の水素ガス含有炭酸カルシウム。
[2]
[A] The hydrogen gas-containing calcium carbonate according to [1], wherein the component has an average particle diameter of 1 to 100 μm.
〔３〕
［ａ］成分が、珊瑚由来の晶析炭酸カルシウムである〔１〕に記載の水素ガス含有炭酸カルシウム。
[3]
[A] The hydrogen gas-containing calcium carbonate according to [1], wherein the component is crystallized calcium carbonate derived from soot.
〔４〕
〔１〕に記載の水素ガス含有炭酸カルシウムを添加して成る食品及び栄養補助食品。
[4]
A food and nutritional supplement obtained by adding the hydrogen carbonate-containing calcium carbonate according to [1].
〔５〕
下記の［ａ］成分
［ａ］成分：貝殻、真珠、風化造礁珊瑚、及び炭酸カルシウムから成る群より選択される１種又は２種以上の粒子、
を、
下記の［ｂ］成分
［ｂ］成分：メタノール、エタノール、プロパノール、単糖類水溶液、二糖類水溶液、有機酸水溶液から成る群より選択される１種又は２種以上、
に浸漬して、１０〜６０ｋＨｚの超音波を１〜６０分間照射することにより、［ｂ］成分を［ａ］成分に付着させる工程と、
［ｂ］成分が付着する［ａ］成分の水分量を１質量％以下とした後、２５０〜５００℃で１０分間〜５時間焼成する工程とを有することを特徴とする〔１〕に記載の水素ガス含有炭酸カルシウムの製造方法。
[5]
The following [a] component [a] component: one or more particles selected from the group consisting of shells, pearls, weathered reef ridges, and calcium carbonate,
The
The following [b] component [b] component: 1 type (s) or 2 or more types selected from the group which consists of methanol, ethanol, propanol, monosaccharide aqueous solution, disaccharide aqueous solution, organic acid aqueous solution,
A step of adhering the [b] component to the [a] component by irradiating with 10 to 60 kHz ultrasonic waves for 1 to 60 minutes,
[B] After adhering the moisture content of the component [a] to which the component [b] adheres to 1% by mass or less, the method includes a step of baking at 250 to 500 ° C. for 10 minutes to 5 hours. A method for producing hydrogen gas-containing calcium carbonate.
〔６〕
［ａ］成分が、珊瑚由来の晶析炭酸カルシウムである〔５〕に記載の水素ガス含有炭酸カルシウムの製造方法。
[6]
[A] The method for producing hydrogen gas-containing calcium carbonate according to [5], wherein the component is crystallized calcium carbonate derived from soot.
本発明の水素ガス含有炭酸カルシウムは、保持されている水素ガスが拡散消失され難い。そのため、長期間に亘って水素ガスを保持させることができる。 In the hydrogen carbonate-containing calcium carbonate of the present invention, the retained hydrogen gas is difficult to diffuse and disappear. Therefore, hydrogen gas can be held for a long time.
本発明の水素ガス含有炭酸カルシウムは、その製造工程において［ａ］成分に［ｂ］成分が含浸され、超音波処理が行われているため、珊瑚、牡蠣殻等の天然由来の炭酸カルシウムを原料として用いる場合であっても、水素ガス含有量を高くすることができる。そのため、本発明の水素ガス含有炭酸カルシウムを摂取する場合、人体内で生成するフリーラジカルを有効に無害化する効果が高い。 Since the hydrogen gas-containing calcium carbonate of the present invention is impregnated with the component [b] in the production process and subjected to ultrasonic treatment, the raw material is calcium carbonate derived from nature such as strawberries and oyster shells. Even when used as, the hydrogen gas content can be increased. Therefore, when ingesting the hydrogen gas-containing calcium carbonate of the present invention, the effect of effectively detoxifying free radicals generated in the human body is high.
本発明の水素ガス含有炭酸カルシウムは、その製造過程において加熱処理されているため、別途の殺菌処理を要しない。そのため、食品原料として衛生的である。 Since the hydrogen gas-containing calcium carbonate of the present invention is heat-treated in the production process, no separate sterilization treatment is required. Therefore, it is hygienic as a food material.
１．水素ガス含有炭酸カルシウム
本発明の水素ガス含有炭酸カルシウムは、下記の［ａ］成分の粒子と、［ａ］成分の粒子内に保持されている水素ガスとから構成される。
1. Hydrogen Gas-Containing Calcium Carbonate The hydrogen gas-containing calcium carbonate of the present invention comprises the following [a] component particles and hydrogen gas retained in the [a] component particles.
（１）［ａ］成分
本発明の水素ガス含有炭酸カルシウムを構成する［ａ］成分の粒子としては、貝殻、真珠、風化造礁珊瑚を粉砕した粒子や、炭酸カルシウムの粒子が挙げられる。これらは単独で用いてもよいし、２種以上を併用してもよい。
(1) [a] component As a particle of the [a] component which comprises the hydrogen gas containing calcium carbonate of this invention, the particle | grains which grind | pulverized the shell, the pearl, the weathered reef shark, and the particle | grains of calcium carbonate are mentioned. These may be used alone or in combination of two or more.
貝殻としては、牡蠣やホタテなどの貝殻が例示される。 Examples of the shell include shells such as oysters and scallops.
貝殻、真珠、風化造礁珊瑚は、骨格をなす炭酸カルシウムと、その層間に蓄積する蛋白質を主とするコンキオリン等の有機物とから構成されている。このコンキオリンは後述する通り、水素ガスの発生源となる。 Shells, pearls, and weathered reef sharks are composed of calcium carbonate, which forms a skeleton, and organic matter such as conchiolin, which is mainly composed of proteins accumulated between the layers. As will be described later, this conchiolin becomes a hydrogen gas generation source.
炭酸カルシウムとしては、沈降炭酸カルシウムや珊瑚由来の晶析炭酸カルシウムが例示される。 Examples of calcium carbonate include precipitated calcium carbonate and crystallized calcium carbonate derived from soot.
沈降炭酸カルシウムはどのような製造方法によって得られるものであっても良く、例えば炭酸ガス反応法、可溶性塩反応法で得られる沈降炭酸カルシウムを用いることができる。また、日本薬局方第１５版に収載される沈降炭酸カルシウムを用いることができる。 The precipitated calcium carbonate may be obtained by any production method, and for example, precipitated calcium carbonate obtained by a carbon dioxide reaction method or a soluble salt reaction method can be used. Precipitated calcium carbonate listed in the Japanese Pharmacopoeia 15th edition can also be used.
珊瑚由来の晶析炭酸カルシウムとは、珊瑚由来の炭酸カルシウムが溶解する水に結晶核を投入して析出させる炭酸カルシウムをいう。珊瑚由来の炭酸カルシウムが溶解する水としては、珊瑚堆積物からなる石灰岩を豊富に含む地層から採取される地下水や湧水が挙げられる。 Crystallized calcium carbonate derived from soot refers to calcium carbonate that is deposited by depositing crystal nuclei in water in which calcium carbonate derived from soot is dissolved. Examples of water in which calcium carbonate derived from dredging dissolves include groundwater and spring water collected from strata containing abundant limestone composed of dredged sediment.
例えば、琉球諸島の地層の一部は、珊瑚堆積物からなる石灰岩地盤で覆われているため、この地層から採取される地下水には炭酸カルシウムが豊富に含まれている。即ち、この地下水は硬度が高く、そのままでは水道水として利用できない。そのため、この地下水は晶析処理により炭酸カルシウムを析出させて、水道水として利用されている。この晶析処理の際に析出される炭酸カルシウムを本発明の［ａ］成分として利用することができる。 For example, a part of the stratum of the Ryukyu Islands is covered with limestone ground consisting of dredged sediments, so the groundwater collected from this strata is rich in calcium carbonate. That is, this groundwater has high hardness and cannot be used as tap water as it is. For this reason, this groundwater is used as tap water by depositing calcium carbonate by crystallization treatment. Calcium carbonate precipitated during this crystallization treatment can be used as the [a] component of the present invention.
［ａ］成分の粒子の平均粒子径は０．１〜１００μｍで、１〜８０μｍが好ましい。１００μｍよりも大きいと、［ｂ］成分（後述）が粒子の中心部まで浸透し難くなり、水素ガスの保持量を高くすることができない。０．１μｍよりも小さいと、内部に保持される［ｂ］成分の量が少なくなり水素ガスの保持量を高くすることができない。 [A] The average particle size of the component particles is 0.1 to 100 μm, preferably 1 to 80 μm. If it is larger than 100 μm, it will be difficult for the component [b] (described later) to penetrate to the center of the particle, and the amount of hydrogen gas retained cannot be increased. If it is smaller than 0.1 μm, the amount of the [b] component held inside becomes small and the amount of hydrogen gas held cannot be increased.
［ａ］成分の比表面積は０．５ｍ２／ｇ以上であることが好ましい。０．５ｍ２／ｇよりも小さいと、水素ガスの保持量が極端に少なくなる。 [A] It is preferable that the specific surface area of a component is 0.5 m < 2 > / g or more. When it is smaller than 0.5 m 2 / g, the amount of hydrogen gas retained becomes extremely small.
（２）［ａ］成分の粒子内に保持される水素ガス
［ａ］成分の粒子内に保持される水素ガスは、コンキオリン等の有機物が熱分解して生成する水素ガスや、後述の［ｂ］成分が熱分解して生成する水素ガスである。この水素ガスは、［ａ］成分の細孔や間隙内に保持される。
(2) Hydrogen gas retained in the particles of [a] component The hydrogen gas retained in the particles of [a] component may be hydrogen gas produced by thermal decomposition of organic matter such as conchiolin, ] Hydrogen gas produced by thermal decomposition of components. This hydrogen gas is held in the pores and gaps of the [a] component.
貝殻、真珠、風化造礁珊瑚は、骨格をなす炭酸カルシウムと、その層間に蓄積する蛋白質を主としたコンキオリン等の有機物とから構成されている。貝殻、真珠、風化造礁珊瑚は、焼成されると前記有機物が熱分解により消失し、炭酸カルシウム骨格に多数の細孔や間隙が形成される。この細孔や間隙内には、酸素が供給されず、局所的に還元的雰囲気となる。そのため、熱処理する雰囲気は酸化的雰囲気であってもよい。この局所的な還元的雰囲気下で前記有機物が熱分解されて生成する水素ガスの一部は、この細孔や間隙内に保持される。 Seashells, pearls, and weathered reef sharks are composed of calcium carbonate, which forms a skeleton, and organic matter, such as conchiolin, mainly composed of proteins accumulated between the layers. When shells, pearls, and weathered reef sharks are fired, the organic matter disappears due to thermal decomposition, and a large number of pores and gaps are formed in the calcium carbonate skeleton. Oxygen is not supplied into the pores and gaps, and a reducing atmosphere is locally formed. Therefore, the atmosphere for heat treatment may be an oxidative atmosphere. A part of the hydrogen gas generated by pyrolyzing the organic substance in this local reducing atmosphere is retained in the pores and gaps.
一方、炭酸カルシウムは水素ガスの発生源である有機物を実質的に含有しない。そのため、［ａ］成分に［ｂ］成分（後述）を付着させて水素ガス発生源とする。 On the other hand, calcium carbonate does not substantially contain an organic substance that is a source of hydrogen gas. Therefore, the [b] component (described later) is attached to the [a] component to form a hydrogen gas generation source.
貝殻、真珠、風化造礁珊瑚は、産出場所や成長条件の違いにより、層間に含まれる有機物の量や組成が一定ではない。そのため、これらを焼成する場合、水素ガス保持量は必ずしも一定範囲に収らない。本発明においては、［ａ］成分として、貝殻、真珠、風化造礁珊瑚を用いる場合であっても、これらに［ｂ］成分を付着させている。これにより、水素ガスの保持量を高めるとともに、水素ガスの保持量を一定化している。 In shells, pearls, and weathered reefs, the amount and composition of organic matter contained between layers is not constant due to differences in production location and growth conditions. Therefore, when these are fired, the hydrogen gas retention amount is not necessarily within a certain range. In the present invention, even when shells, pearls, and weathered reef ridges are used as the [a] component, the [b] component is attached thereto. Thereby, the holding amount of hydrogen gas is increased and the holding amount of hydrogen gas is made constant.
即ち、［ａ］成分として貝殻、真珠、風化造礁珊瑚を使用する場合には、その層間に蓄積する蛋白質を主としたコンキオリン等の有機物と、［ｂ］成分とが水素ガスの発生源となる。一方、炭酸カルシウムを使用する場合には、実質的に［ｂ］成分のみが水素ガスの発生源となる。 That is, when shells, pearls, or weathered reef ridges are used as the [a] component, organic substances such as conchiolin mainly consisting of proteins accumulated between the layers, and the [b] component are hydrogen gas generation sources. Become. On the other hand, when calcium carbonate is used, only the component [b] is a hydrogen gas generation source.
本発明の水素ガス含有炭酸カルシウムには、［ａ］成分１ｇあたり、２５℃において０．１〜５０μＬの水素ガスが保持されている。 In the hydrogen gas-containing calcium carbonate of the present invention, 0.1 to 50 μL of hydrogen gas is held at 25 ° C. per 1 g of the [a] component.
この水素ガス含有炭酸カルシウムは、保持されている水素ガスが大気中において拡散消失され難い。本発明の水素ガス含有炭酸カルシウムは、温度２５℃、湿度５０％、大気圧下の開放系において、製造後６ヶ月間保管した後における水素ガスの残存率が５０％以上であり、好ましくは８０％以上であり、特に好ましくは９０％以上である。同条件下、水素ガスの残存率が５０％未満である物は本発明の範囲外である。 This hydrogen gas-containing calcium carbonate is unlikely to diffuse and disappear the retained hydrogen gas in the atmosphere. The hydrogen gas-containing calcium carbonate of the present invention has a residual ratio of hydrogen gas of 50% or more after storage for 6 months after production in an open system at a temperature of 25 ° C., a humidity of 50% and atmospheric pressure, preferably 80 % Or more, and particularly preferably 90% or more. Those having a residual ratio of hydrogen gas of less than 50% under the same conditions are outside the scope of the present invention.
２．水素ガス含有炭酸カルシウムの製造方法
本発明の水素ガス含有炭酸カルシウムは、上述の［ａ］成分に後述の［ｂ］成分を付着させ、これを乾燥及び焼成することにより製造される。
2. Method for Producing Hydrogen Gas-Containing Calcium Carbonate The hydrogen gas-containing calcium carbonate of the present invention is produced by adhering the [b] component described later to the above-mentioned [a] component, and drying and baking it.
（１）［ｂ］成分
本発明の水素ガス含有炭酸カルシウムの製造に用いる［ｂ］成分は、メタノール、エタノール、プロパノール等のアルコール類や、Ｄ−グルコースやＤ−フラクトース等の単糖類、マルトースやセルビオース、サッカロース等の二糖類、クエン酸やリンゴ酸等の有機酸である。アルコール類は無水アルコールであっても含水アルコールであっても良い。これら水素化合物は不純物を実質的に含まない物を用いることが好ましい。これらは単独で用いても、２種以上を組み合わせて用いても良い。
(1) [b] component [b] component used for manufacture of the hydrogen gas containing calcium carbonate of this invention is alcohol, such as methanol, ethanol, and propanol, monosaccharides, such as D-glucose and D-fructose, maltose, Disaccharides such as cellobiose and saccharose, and organic acids such as citric acid and malic acid. The alcohols may be anhydrous alcohols or hydrous alcohols. These hydrogen compounds are preferably used which are substantially free of impurities. These may be used alone or in combination of two or more.
（２）［ｂ］成分の［ａ］成分への付着
［ａ］成分に［ｂ］成分を付着させる方法としては、［ｂ］成分がアルコール類の場合はそのままあるいは水で希釈して［ａ］成分に付着させる。［ｂ］成分が単糖類水溶液、二糖類水溶液又は有機酸水溶液の場合はそのまま［ａ］成分に付着させる。この水溶液中における単糖類、二糖類又は有機酸の濃度は、０．００５〜０．５ｍｏｌ／Ｌが好ましく、０．０１〜０．１ｍｏｌ／Ｌが特に好ましい。
(2) Adhesion of [b] component to [a] component As a method of adhering [b] component to [a] component, when [b] component is an alcohol, it is diluted as it is or with water [a] ] Adhere to the component. When the component [b] is a monosaccharide aqueous solution, a disaccharide aqueous solution, or an organic acid aqueous solution, it is directly attached to the [a] component. The concentration of monosaccharide, disaccharide or organic acid in this aqueous solution is preferably 0.005 to 0.5 mol / L, particularly preferably 0.01 to 0.1 mol / L.
付着は、［ｂ］成分中に、［ａ］成分を浸漬することにより行う。浸漬の際には、［ａ］成分全体に［ｂ］成分が十分に浸る量の［ｂ］成分を用いる。浸漬時間は５分間〜２０時間が好ましい。浸漬温度は特に制限がない。 Adhesion is performed by immersing the [a] component in the [b] component. In the immersion, the [b] component is used in such an amount that the [b] component is sufficiently immersed in the entire [a] component. The immersion time is preferably 5 minutes to 20 hours. The immersion temperature is not particularly limited.
浸漬の際には１０〜６０ｋＨｚの超音波を１〜６０分間照射する。これにより、［ａ］成分に形成されている細孔に［ｂ］成分を十分に含浸させることができる。その結果、得られる水素ガス含有炭酸カルシウムは、水素ガス保持量が高くなるとともに、保持される水素ガスが拡散消失し難い。 During the immersion, an ultrasonic wave of 10 to 60 kHz is irradiated for 1 to 60 minutes. Thereby, the pore formed in the [a] component can be sufficiently impregnated with the [b] component. As a result, the hydrogen gas-containing calcium carbonate obtained has a high hydrogen gas retention amount and the retained hydrogen gas is difficult to diffuse and disappear.
上記［ｂ］成分が含浸付着する［ａ］成分は、濾過やデカンテーション等の分離手段により余分な［ｂ］成分が除去された後、乾燥させることにより、［ａ］成分に［ｂ］成分が保持される。乾燥方法は、真空乾燥や噴霧乾燥、凍結乾燥、ドラムドライヤによる乾燥等、公知の方法で行うことができる。この際、［ａ］成分の残存水分は１質量％以下とすることが好ましい。 The [a] component to which the above [b] component is impregnated and adhered is removed after the excess [b] component is removed by separation means such as filtration or decantation, and then dried to obtain the [b] component. Is retained. The drying method can be performed by a known method such as vacuum drying, spray drying, freeze drying, or drying with a drum dryer. At this time, the residual water content of the component [a] is preferably 1% by mass or less.
（３）［ｂ］成分が保持される［ａ］成分の焼成
上記［ｂ］成分が保持されている［ａ］成分は焼成することにより、コンキオリン等の有機物や［ｂ］成分（以下、これらを総称して「水素源物質」ともいう）が熱分解される。熱分解により発生する水素ガスは［ａ］成分に保持される。焼成温度は、２５０〜５００℃で、３５０℃程度が好ましい。この範囲の温度に加熱することで、水素源物質は熱分解され、生成する水素ガスが［ａ］成分、特に［ａ］成分粒子の細孔部に物理的に保持される。焼成時間は焼成量や焼成に用いる装置によっても異なるが、およそ１０分間〜５時間である。
(3) Firing of the [a] component in which the [b] component is retained The [a] component in which the [b] component is retained is calcined to produce an organic substance such as conchiolin or the [b] component (hereinafter referred to as these Are also collectively referred to as “hydrogen source materials”). Hydrogen gas generated by pyrolysis is held in the [a] component. The firing temperature is 250 to 500 ° C, preferably about 350 ° C. By heating to a temperature in this range, the hydrogen source material is thermally decomposed, and the generated hydrogen gas is physically held in the pores of the [a] component, particularly the [a] component particles. The firing time is approximately 10 minutes to 5 hours, although it varies depending on the firing amount and the apparatus used for firing.
焼成は窒素ガス等の不活性雰囲気や、大気等の酸化雰囲気で行うことができる。［ａ］成分に形成される細孔は、マイクロポアからメゾポアの大きさと推定できる。本発明の水素ガス含有炭酸カルシウムは、炭酸カルシウムの細孔内で熱分解が行われる。熱分解時、細孔内は細孔外部から酸素が供給されにくくなるため、局所的に還元的雰囲気となる。そのため、窒素ガス等の還元的雰囲気で処理しなくても良く、製造コストや簡便さに優れる。細孔内の水素源物質は、この還元的雰囲気で熱分解され、生成する水素ガスが細孔内に物理的に含有されると考えられる。 Firing can be performed in an inert atmosphere such as nitrogen gas or an oxidizing atmosphere such as air. The pores formed in the component [a] can be estimated from the micropores to the size of the mesopores. The hydrogen gas-containing calcium carbonate of the present invention is thermally decomposed in the pores of calcium carbonate. During pyrolysis, the inside of the pores is less likely to be supplied with oxygen from the outside of the pores, resulting in a locally reducing atmosphere. Therefore, it is not necessary to perform the treatment in a reducing atmosphere such as nitrogen gas, and the manufacturing cost and simplicity are excellent. It is considered that the hydrogen source material in the pores is thermally decomposed in this reducing atmosphere, and the generated hydrogen gas is physically contained in the pores.
３．本発明の水素ガス含有炭酸カルシウムの利用
本発明の水素ガス含有炭酸カルシウムは、１日あたり３００〜６００ｍｇ（カルシウム換算）を摂取することが好ましい。本発明の水素ガス含有炭酸カルシウムは、顆粒剤やカプセル剤に加工してサプリメントとしても良いし、パンやクッキー等の食品に添加しても良い。本発明の水素ガス含有炭酸カルシウムは、大気中で１００℃程度に加熱しても水素ガスが放出されることはない。
3. Use of hydrogen gas-containing calcium carbonate of the present invention The hydrogen gas-containing calcium carbonate of the present invention preferably takes 300 to 600 mg (calculated in terms of calcium) per day. The hydrogen gas-containing calcium carbonate of the present invention may be processed into granules or capsules to be a supplement, or may be added to foods such as bread and cookies. The hydrogen gas-containing calcium carbonate of the present invention does not release hydrogen gas even when heated to about 100 ° C. in the atmosphere.
本発明の水素ガス含有炭酸カルシウムは、大気中に放置している間は、水素ガスは長期間にわたり殆ど放出されない。しかし、水中に存在させた場合、水素ガスは液相中で細孔内と細孔外の濃度差により放出される。そのため、水素ガスは水素ガスの担体である［ａ］成分の粒子表面から順次水中に拡散される。［ａ］成分の粒子表面では水素ガス濃度は飽和点に達しているか過飽和状態になっているものと考えられる。局所的には水素ガス濃度は極めて高くなっていると推定される。従って、水素ガスは［ａ］成分１ｇ当り０．１μＬ（２５℃）以上含有されていれば、活性酸素を打ち消すに充分な量であるといえる。 While the hydrogen gas-containing calcium carbonate of the present invention is left in the atmosphere, hydrogen gas is hardly released over a long period of time. However, when it is present in water, hydrogen gas is released in the liquid phase due to a difference in concentration between the pores inside and outside the pores. Therefore, hydrogen gas is sequentially diffused into water from the particle surface of the [a] component that is a carrier of hydrogen gas. It is considered that the hydrogen gas concentration reaches the saturation point or is supersaturated on the particle surface of the component [a]. Locally, the hydrogen gas concentration is estimated to be extremely high. Therefore, it can be said that hydrogen gas is an amount sufficient to cancel active oxygen if it is contained in an amount of 0.1 μL (25 ° C.) or more per 1 g of the [a] component.
本発明の水素ガス含有炭酸カルシウムの水素ガス含有量は、一定量の該水素ガス含有炭酸カルシウムを密閉容器に入れて一定量の純水に溶かし、一定容積の気相を一定時間ごとに採取してガスクロマトグラフで分析することにより定量することができる。 The hydrogen gas content of the hydrogen gas-containing calcium carbonate of the present invention is such that a certain amount of the hydrogen gas-containing calcium carbonate is placed in a sealed container and dissolved in a certain amount of pure water, and a certain volume of gas phase is sampled at regular intervals. It can be quantified by analyzing with a gas chromatograph.
（実施例１）
平均粒径５０μｍの珊瑚由来の晶析炭酸カルシウム粉１０００ｇをバットに入れ、９５％（Ｖ／Ｖ）エタノール４００ｍＬをバットに注ぎ、３５ｋＨｚの超音波を１０分間照射してから１０時間静置した。この晶析炭酸カルシウム粉を風乾後、空気中で３５０℃の電気炉を用いて３時間加熱し、水素ガス含有炭酸カルシウムを得た。
(Example 1)
1000 g of crystallized calcium carbonate powder derived from cocoons having an average particle size of 50 μm was put into a vat, 400 mL of 95% (V / V) ethanol was poured into the vat, and 35 kHz ultrasonic waves were irradiated for 10 minutes and allowed to stand for 10 hours. The crystallized calcium carbonate powder was air-dried and then heated in air using an electric furnace at 350 ° C. for 3 hours to obtain hydrogen gas-containing calcium carbonate.
この水素ガス含有炭酸カルシウム３．０ｇを３３ｍｌの容器に取り、純水１５ｍｌを加えて密閉し、３６℃に加温後、容器を激しく振って容器下部に沈殿した炭酸カルシウム粉体を分散させた。その後、容器内の気相０．５ｍｌをガスクロマトグラフに注入して水素ガスの定量分析を行った。本分析の分析条件は以下の通りである。この水素ガス含有炭酸カルシウムは、温度２５℃、湿度５０％、大気圧下の開放系において保存して、１ヶ月後、３ヶ月後及び６ヶ月後の水素ガス含有量を同様に測定した。分析結果は表１に示した。 Take 3.0 g of this hydrogen gas-containing calcium carbonate in a 33 ml container, add 15 ml of pure water and seal it. After warming to 36 ° C., shake the container vigorously to disperse the precipitated calcium carbonate powder at the bottom of the container. . Thereafter, 0.5 ml of the gas phase in the container was injected into a gas chromatograph to perform quantitative analysis of hydrogen gas. The analysis conditions for this analysis are as follows. This hydrogen gas-containing calcium carbonate was stored in an open system at a temperature of 25 ° C., a humidity of 50%, and atmospheric pressure, and the hydrogen gas content after 1 month, 3 months and 6 months was measured in the same manner. The analysis results are shown in Table 1.
ガスクロマトグラフ分析条件
ガスクロマトグラフ：島津 ＧＣ１４ＡＴ
データ処理装置：島津クロマトパック Ｃ−Ｒ７Ａ
カラム：モレキュラーシーブ−５Ａ
カラム温度：７５℃
検出器：ＴＣＤ
検出器温度：７０℃、
電流値：８０ｍＡ
キャリアガス：アルゴン、 アッテネーション：２０、
試料注入量：０．５ｍｌ、ＰＡ＝８
（実施例２）
実施例１における平均粒径５０μｍの珊瑚由来の晶析炭酸カルシウム粉を、平均粒径５０μｍの風化造礁珊瑚粉に変更して実施例１と同様に操作し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
Gas chromatograph analysis conditions Gas chromatograph: Shimadzu GC14AT
Data processor: Shimadzu Chromatopack C-R7A
Column: Molecular sieve-5A
Column temperature: 75 ° C
Detector: TCD
Detector temperature: 70 ° C.
Current value: 80 mA
Carrier gas: Argon, Attenuation: 2 0 ,
Sample injection volume: 0.5 ml, PA = 8
(Example 2)
The crystallized calcium carbonate powder derived from the cocoon having an average particle diameter of 50 μm in Example 1 was changed to a weathered reef cocoon powder having an average particle diameter of 50 μm and operated in the same manner as in Example 1 to obtain hydrogen gas-containing calcium carbonate. . Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（実施例３）
実施例１における平均粒径５０μｍの珊瑚由来の晶析炭酸カルシウム粉を、平均粒径８０μｍのカキ殻粉に変更して実施例１と同様に操作し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
(Example 3)
The crystallized calcium carbonate powder derived from soot having an average particle diameter of 50 μm in Example 1 was changed to oyster shell powder having an average particle diameter of 80 μm and operated in the same manner as in Example 1 to obtain hydrogen gas-containing calcium carbonate. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（実施例４）
実施例１における９５％（Ｖ／Ｖ）エタノール４００ｍＬを、０．０１ｍｏｌ／Ｌのグルコース水溶液に変更して実施例１と同様に操作し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
Example 4
400 mL of 95% (V / V) ethanol in Example 1 was changed to a 0.01 mol / L aqueous glucose solution and operated in the same manner as in Example 1 to obtain hydrogen gas-containing calcium carbonate. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（実施例５）
実施例２における９５％（Ｖ／Ｖ）エタノール４００ｍＬを、０．０１ｍｏｌ／Ｌのグルコース水溶液に変更して実施例１と同様に操作し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
(Example 5)
400 mL of 95% (V / V) ethanol in Example 2 was changed to a 0.01 mol / L aqueous glucose solution and operated in the same manner as in Example 1 to obtain hydrogen gas-containing calcium carbonate. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（実施例６）
実施例３における９５％（Ｖ／Ｖ）エタノール４００ｍＬを、０．０１ｍｏｌ／Ｌのグルコース水溶液に変更して実施例１と同様に操作し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
(Example 6)
400 mL of 95% (V / V) ethanol in Example 3 was changed to a 0.01 mol / L aqueous glucose solution and operated in the same manner as in Example 1 to obtain hydrogen gas-containing calcium carbonate. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（比較例１）
平均粒径５０μｍの風化造礁珊瑚粉１０００ｇを空気中で３５０℃の電気炉を用いて３時間加熱し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
(Comparative Example 1)
1000 g of weathered reef forming powder having an average particle size of 50 μm was heated in air using an electric furnace at 350 ° C. for 3 hours to obtain hydrogen gas-containing calcium carbonate. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（比較例２）
平均粒径８０μｍのカキ殻粉１０００ｇを空気中で３５０℃の電気炉を用いて３時間加熱し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
(Comparative Example 2)
1000 g of oyster shell powder having an average particle size of 80 μm was heated in air using an electric furnace at 350 ° C. for 3 hours to obtain hydrogen gas-containing calcium carbonate. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
（比較例３−８）
３５ｋＨｚ超音波の１０分間の照射を行わない他は、それぞれ実施例１−６と同様に操作し、水素ガス含有炭酸カルシウムを得た。この水素ガス含有炭酸カルシウムを試料とし、実施例１と同様の方法により水素ガス含有量を測定し、結果を表１に示した。
(Comparative Example 3-8)
A hydrogen gas-containing calcium carbonate was obtained in the same manner as in Example 1-6 except that 35-kHz ultrasonic waves were not irradiated for 10 minutes. Using this hydrogen gas-containing calcium carbonate as a sample, the hydrogen gas content was measured by the same method as in Example 1, and the results are shown in Table 1.
実施例１〜６の水素ガス含有炭酸カルシウムの水素ガス含有量は、製造直後と６月経過後とで殆ど変化しなかった。一方、比較例１〜８の水素ガス含有炭酸カルシウムの水素ガス含有量は、経時的に低下した。 The hydrogen gas content of the hydrogen gas-containing calcium carbonate of Examples 1 to 6 hardly changed between immediately after production and after 6 months. On the other hand, the hydrogen gas content of the hydrogen gas-containing calcium carbonate of Comparative Examples 1 to 8 decreased with time.
（実施例７）
実施例１で得た水素ガス含有炭酸カルシウム５０ｍｇをハードカプセルに充填してサプリメントを得た。このサプリメントは違和感なく服用することができた。
(Example 7)
A supplement was obtained by filling 50 mg of the hydrogen gas-containing calcium carbonate obtained in Example 1 into a hard capsule. I was able to take this supplement without any discomfort.
Claims (6)
［ａ］成分：貝殻、真珠、風化造礁珊瑚、炭酸カルシウムから成る群より選択される１種又は２種以上の粒子
と、
前記［ａ］成分の粒子内に保持される水素ガスと、から成る水素ガス含有炭酸カルシウムであって、
前記［ａ］成分１ｇあたりに、２５℃において０．１〜５０μＬの水素ガスが保持されて成り、
温度２５℃、湿度５０％、大気圧下の開放状態において製造後６ヶ月間保存した後の水素ガス残存量が５０％以上であることを特徴とする水素ガス含有炭酸カルシウム。 The following [a] component,
[A] component: 1 type or 2 or more types of particle | grains selected from the group which consists of a shell, a pearl, a weathered reef shark, a calcium carbonate,
A hydrogen gas-containing calcium carbonate comprising hydrogen gas held in the particles of the component [a],
0.1 g to 50 μL of hydrogen gas is held at 25 ° C. per 1 g of the component [a],
A hydrogen gas-containing calcium carbonate characterized by having a hydrogen gas residual amount of 50% or more after storage for 6 months after production in an open state at a temperature of 25 ° C., a humidity of 50%, and atmospheric pressure.
［ａ］成分：貝殻、真珠、風化造礁珊瑚、及び炭酸カルシウムから成る群より選択される１種又は２種以上の粒子、
を、
下記の［ｂ］成分
［ｂ］成分：メタノール、エタノール、プロパノール、単糖類水溶液、二糖類水溶液、有機酸水溶液から成る群より選択される１種又は２種以上、
に浸漬して、１０〜６０ｋＨｚの超音波を１〜６０分間照射することにより、［ｂ］成分を［ａ］成分に付着させる工程と、
［ｂ］成分が付着する［ａ］成分の水分量を１質量％以下とした後、２５０〜５００℃で１０分間〜５時間焼成する工程とを有することを特徴とする〔１〕に記載の水素ガス含有炭酸カルシウムの製造方法。 The following [a] component [a] component: one or more particles selected from the group consisting of shells, pearls, weathered reef ridges, and calcium carbonate,
The
The following [b] component [b] component: 1 type (s) or 2 or more types selected from the group which consists of methanol, ethanol, propanol, monosaccharide aqueous solution, disaccharide aqueous solution, organic acid aqueous solution,
A step of adhering the [b] component to the [a] component by irradiating with 10 to 60 kHz ultrasonic waves for 1 to 60 minutes,
[B] After adhering the moisture content of the component [a] to which the component [b] adheres to 1% by mass or less, the method includes a step of baking at 250 to 500 ° C. for 10 minutes to 5 hours. A method for producing hydrogen gas-containing calcium carbonate.
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