JP2019182699A - Hydrogen generating material and manufacturing method therefor - Google Patents
Hydrogen generating material and manufacturing method therefor Download PDFInfo
- Publication number
- JP2019182699A JP2019182699A JP2018074253A JP2018074253A JP2019182699A JP 2019182699 A JP2019182699 A JP 2019182699A JP 2018074253 A JP2018074253 A JP 2018074253A JP 2018074253 A JP2018074253 A JP 2018074253A JP 2019182699 A JP2019182699 A JP 2019182699A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- resin
- hydrogen generating
- water
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 194
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 194
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 98
- 229920005989 resin Polymers 0.000 claims abstract description 96
- 239000011347 resin Substances 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011247 coating layer Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 238000010828 elution Methods 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 18
- -1 fluororesin Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 229910012375 magnesium hydride Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 229920013716 polyethylene resin Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ZGLFRTJDWWKIAK-UHFFFAOYSA-M [2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OC(C)(C)C)C1=CC=CC=C1 ZGLFRTJDWWKIAK-UHFFFAOYSA-M 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- AYBCUKQQDUJLQN-UHFFFAOYSA-N hydridoberyllium Chemical compound [H][Be] AYBCUKQQDUJLQN-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Description
本発明は、新規な水素発生材料及びその製造方法に関する。より具体的には、水又は水を含む液体と接触した際に水素を発生する材料に関する The present invention relates to a novel hydrogen generating material and a method for producing the same. More specifically, it relates to a material that generates hydrogen when contacted with water or a liquid containing water.
近年、水素ガスあるいは水素を含む水又は液体を人体に作用させた際に、人体にいろいろな有益な効能が得られることが明らかとなりつつある。このため、水素を発生させる材料、水素を密封した製品等が種々提案されている。 In recent years, it has become clear that various beneficial effects can be obtained in the human body when hydrogen gas or water or liquid containing hydrogen is applied to the human body. For this reason, various materials that generate hydrogen, products sealed with hydrogen, and the like have been proposed.
例えば、容器の内部に収容された液状物に対して、水素添加するための水素発生機能付き容器であって、樹脂中に、粒子状水素発生剤を含んでなる水素発生層を、前記容器の内表面、および前記容器の内部に配置されたノズルの表面、あるいはいずれか一方の表面に、それぞれ全面的または部分的に備えることを特徴とする水素発生機能付き容器が提案されている（特許文献１）。 For example, a container with a hydrogen generation function for adding hydrogen to a liquid substance contained in the container, wherein a hydrogen generation layer containing a particulate hydrogen generator in a resin is provided in the container. There has been proposed a container with a hydrogen generating function, characterized in that it is provided on the inner surface and / or the surface of a nozzle disposed inside the container, either entirely or partially (Patent Document). 1).
また例えば、水又は水性組成物と接触して使用されるものである成形体であって、水又は水性組成物と接触する前記成形体の全部又は一部は、水と接触することによって分子状水素を発生する成分からなるものであることを特徴とする成形体が知られている（特許文献２）。 Also, for example, a molded product that is used in contact with water or an aqueous composition, and all or part of the molded product that is in contact with water or the aqueous composition is molecular by contacting with water. A molded body characterized by comprising a component that generates hydrogen is known (Patent Document 2).
しかしながら、これら従来の技術では、水素発生粒子が脱落しないように水素発生層上に表面層が積層されている。このような構造では、水素発生粒子と水との反応が不十分となることがあり、その結果として所定量の水素を発生させることが困難となるおそれがある。 However, in these conventional techniques, the surface layer is laminated on the hydrogen generation layer so that the hydrogen generation particles do not fall off. In such a structure, the reaction between the hydrogen generating particles and water may be insufficient, and as a result, it may be difficult to generate a predetermined amount of hydrogen.
一方、水素発生層が水と直接に接触できるように、水素発生層と水との間に層を設けない構造もある。この場合には、水との反応が良好に行われるものの、水素発生粒子の脱落のおそれがあるほか、水素発生粒子（水素発生剤）自体を構成する成分も水中に溶出しやすくなる。すなわち、水素発生粒子自体の一部が露出した状態となることにより、水素発生粒子を構成する成分がイオン化して溶け出すことがある。例えば、水素発生粒子として代表的な水素化マグネシウムは、水中へのマグネシウムイオンの溶出に伴い、水との反応の副産物として水酸化マグネシウムが生成される。このような副産物は、内容物を変質させたり、商品価値を低下させることがある。 On the other hand, there is also a structure in which no layer is provided between the hydrogen generation layer and water so that the hydrogen generation layer can be in direct contact with water. In this case, although the reaction with water is carried out satisfactorily, there is a risk that the hydrogen generating particles may fall off, and the components constituting the hydrogen generating particles (hydrogen generating agent) themselves are easily eluted into the water. That is, when a part of the hydrogen generating particle itself is exposed, the components constituting the hydrogen generating particle may be ionized and dissolved. For example, magnesium hydride, which is representative of hydrogen generating particles, produces magnesium hydroxide as a by-product of the reaction with water with the elution of magnesium ions into water. Such by-products may alter the contents and reduce the commercial value.
従って、本発明の主な目的は、水素を良好に発生させる一方で、水素発生源を構成する成分の溶出が効果的に抑制された水素発生材料を提供することにある。 Accordingly, a main object of the present invention is to provide a hydrogen generating material in which elution of components constituting a hydrogen generating source is effectively suppressed while hydrogen is generated satisfactorily.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定の構造を有する材料が上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that a material having a specific structure can achieve the above object, and has completed the present invention.
すなわち、本発明は、下記の水素発生材料及びその製造方法に係る。
１． 水と接触することにより水素を発生する材料であって、
（１）ａ）水と反応して水素を発生し得る水素発生粒子、ｂ）被覆用樹脂及びｃ）マトリックス用樹脂を含み、
（２）少なくとも当該材料表面から突出する水素発生粒子の表面が被覆用樹脂を含む被覆層で覆われている、
ことを特徴とする水素発生材料。
２． 前記水素発生粒子が、金属及び水素化金属の少なくとも１種である、前記項１に記載の水素発生材料。
３． マトリックス用樹脂が、ポリオレフィン樹脂、ポリエステル樹脂、ポリアミド樹脂、ウレタン樹脂、フッ素樹脂、エポキシ樹脂、ポリエチレングリコール及びポリエチレンオキサイドの少なくとも１種である、前記項１に記載の水素発生材料。
４． 被覆用樹脂が、ポリオレフィン樹脂及びポリアミド樹脂の少なくとも１種である、前記項１に記載の水素発生材料。
５． 前記水素発生粒子の体積平均粒子径が１〜１００μｍである、前記項１に記載の水素発生材料。
６． 形態がフィルム状である、前記項１に記載の水素発生材料。
７． 水と接触することにより水素を発生する材料を製造する方法であって、
（１）ａ）水と反応して水素を発生し得る水素発生粒子及びｂ）被覆用樹脂とを含む混合物を調製する工程、
（２）前記混合物をマトリックス用樹脂と混合する工程
を含むことを特徴とする水素発生材料の製造方法。
That is, this invention relates to the following hydrogen generating material and its manufacturing method.
1. A material that generates hydrogen by contact with water,
(1) a) hydrogen generating particles capable of generating hydrogen by reacting with water, b) a coating resin and c) a matrix resin,
(2) At least the surface of the hydrogen generating particles protruding from the material surface is covered with a coating layer containing a coating resin.
A hydrogen generating material characterized by that.
2. Item 2. The hydrogen generating material according to Item 1, wherein the hydrogen generating particles are at least one of a metal and a metal hydride.
3. Item 2. The hydrogen generating material according to Item 1, wherein the matrix resin is at least one of polyolefin resin, polyester resin, polyamide resin, urethane resin, fluororesin, epoxy resin, polyethylene glycol, and polyethylene oxide.
4). Item 2. The hydrogen generating material according to Item 1, wherein the coating resin is at least one of a polyolefin resin and a polyamide resin.
5. Item 2. The hydrogen generating material according to Item 1, wherein the hydrogen generating particles have a volume average particle diameter of 1 to 100 µm.
6). Item 2. The hydrogen generating material according to Item 1, wherein the form is a film.
7). A method for producing a material that generates hydrogen by contact with water,
(1) a) preparing a mixture containing hydrogen generating particles capable of generating hydrogen by reacting with water and b) a coating resin;
(2) A method for producing a hydrogen generating material, comprising a step of mixing the mixture with a matrix resin.
本発明によれば、水素を良好に発生させる一方で、水素発生源を構成する成分の溶出が効果的に抑制された水素発生材料を提供することができる。特に、本発明の水素発生材料では、少なくとも当該材料表面から突出する水素発生粒子の表面が被覆用樹脂を含む被覆層で覆われているという構成を備えることによって、水分と反応して水素を発生する一方で、水素供給先と水素発生層との間に必ずしも介在層を有する必要が無い。そのため、水素供給先に水素を好適に供給できるとともに、設計の自由度を高めることができるため、様々な用途に幅広く用いることができる。 ADVANTAGE OF THE INVENTION According to this invention, while generating hydrogen favorably, the elution of the component which comprises a hydrogen generation source can be provided effectively, and the hydrogen generating material can be provided. In particular, in the hydrogen generating material of the present invention, at least the surface of the hydrogen generating particles protruding from the material surface is covered with a coating layer containing a coating resin, thereby generating hydrogen by reacting with moisture. On the other hand, it is not always necessary to have an intervening layer between the hydrogen supply destination and the hydrogen generation layer. For this reason, hydrogen can be suitably supplied to the hydrogen supply destination, and the degree of freedom in design can be increased, so that it can be widely used for various applications.
１．水素発生材料
本発明の水素発生材料（本発明材料）は、水と接触することにより水素を発生する材料であって、
（１）ａ）水と反応して水素を発生し得る水素発生粒子、ｂ）被覆用樹脂及びｃ）マトリックス用樹脂を含み、
（２）少なくとも当該材料表面から突出する水素発生粒子の表面が被覆用樹脂を含む被覆層で覆われている、
ことを特徴とする。
1. Hydrogen generating material The hydrogen generating material of the present invention (the material of the present invention) is a material that generates hydrogen by contact with water,
(1) a) hydrogen generating particles capable of generating hydrogen by reacting with water, b) a coating resin and c) a matrix resin,
(2) At least the surface of the hydrogen generating particles protruding from the material surface is covered with a coating layer containing a coating resin.
It is characterized by that.
シート状の本発明材料の断面構造の一例のイメージ図を図１に示す。図１においては、１つの水素発生粒子３０の表面が被覆用樹脂を含む被覆層２０で覆われた構造を有している。別の構造として、図４に示すように、複数の水素発生粒子３０が被覆用樹脂を含む被覆層２０中に含まれた構造（いわゆるコンパウンドの形態）をとっていても良い。いずれの場合も、被覆層２０中には、本発明の効果を妨げない限り、その他の樹脂（例えばマトリックス用樹脂）等が含まれていなくても良いし、含まれていても良い。 FIG. 1 shows an image of an example of a cross-sectional structure of the sheet-like material of the present invention. In FIG. 1, the surface of one hydrogen generating particle 30 is covered with a coating layer 20 containing a coating resin. As another structure, as shown in FIG. 4, a structure (so-called compound form) in which a plurality of hydrogen generating particles 30 are included in a coating layer 20 including a coating resin may be employed. In any case, the coating layer 20 may or may not contain other resin (for example, matrix resin) or the like as long as the effect of the present invention is not hindered.
本発明材料では、少なくとも当該材料表面から突出する水素発生粒子の表面が被覆用樹脂を含む被覆層で覆われている。図５には、本発明材料表面から突出した水素発生粒子の断面構造の模式図を示す。図５に示すように、水素発生粒子３０は、本発明材料表面１０ａ（特に図５中の破線部）から突き出ており、少なくともその突き出た部分が被覆層２０で覆われている。 In the material of the present invention, at least the surface of the hydrogen generating particles protruding from the material surface is covered with a coating layer containing a coating resin. FIG. 5 shows a schematic diagram of a cross-sectional structure of the hydrogen generating particles protruding from the surface of the material of the present invention. As shown in FIG. 5, the hydrogen generating particles 30 protrude from the material surface 10 a of the present invention (particularly, the broken line portion in FIG. 5), and at least the protruding portion is covered with the coating layer 20.
被覆層２０で覆われた水素発生粒子３０は、マトリックス用樹脂を含むマトリックス１０中に分散した状態となっている。この場合、本発明材料表面から突出している水素発生粒子が被覆層に覆われていれば良いので、例えばマトリックス中に完全に埋まっている水素発生粒子の表面は必ずしも被覆層で覆われていなくても良い。例えば、水素発生粒子３０がマトリックス１０（マトリックス用樹脂）に直に接触した状態で分散されていても良い。 The hydrogen generating particles 30 covered with the coating layer 20 are dispersed in the matrix 10 containing the matrix resin. In this case, the hydrogen generating particles protruding from the surface of the material of the present invention need only be covered with the coating layer. For example, the surface of the hydrogen generating particles completely embedded in the matrix is not necessarily covered with the coating layer. Also good. For example, the hydrogen generating particles 30 may be dispersed while being in direct contact with the matrix 10 (matrix resin).
このように、本発明材料では、当該材料表面から突出した水素発生粒子群のほぼ全部が被覆層で覆われているので、当該材料表面に水が接触した場合、水素発生粒子から水素を発生させる一方で、水素発生粒子自体を構成する成分の水への溶出を効果的に抑制ないしは防止することができる。特に、本発明の製造方法により得られた本発明材料においては、予め水素発生粒子を被覆層で覆ったうえで樹脂Ｂ中に分散させるので、水素発生粒子どうしの凝集を回避しつつ、当該材料中に均一に水素発生粒子を分布させることができるので、より効果的に水素を発生させることができる。 As described above, in the material of the present invention, since almost all of the hydrogen generating particle group protruding from the material surface is covered with the coating layer, hydrogen is generated from the hydrogen generating particle when water contacts the surface of the material. On the other hand, it is possible to effectively suppress or prevent elution of components constituting the hydrogen generating particles themselves into water. In particular, in the material of the present invention obtained by the production method of the present invention, the hydrogen generating particles are previously covered with a coating layer and then dispersed in the resin B, so that the material is avoided while avoiding aggregation of the hydrogen generating particles. Since the hydrogen generating particles can be uniformly distributed therein, hydrogen can be generated more effectively.
本発明材料において、その発生した水素を利用する対象（水素供給先）としては、本発明材料と直接又は間接的に接触させて水素を供給する対象であれば良い。特に、水素の作用（例えば還元作用）により物性を維持ないしは改善できるものが好ましい。また、水素供給先は、水又は水を含む液体であっても良いし、水を含む固体あるいは気体であっても良い。さらに、水素供給先は、純水のほか、水溶液、水分散液等のいずれであっても良い。従って、例えばａ）飲料、食肉類、魚介類、野菜、果物等の食材、ｂ）前記食材を原材料とする加工食品のほか、例えば生花、菌類、細菌類、植物の種子、輸血用血液、輸液、風呂水、洗濯水、洗剤、大気、創傷被覆材、化粧品、オムツ、ペット用飲料、飼育水槽水、微生物、土壌、餌、室内空間、人体、動物、植物等が水素供給先として挙げられる。これらは、水素供給先であると同時に水素発生材料への水分供給源にもなり得るが、水分供給源と水素供給先とが異なっていても良い。特に、水素供給先は、水素発生材料への水分供給源であることが好ましい。 In the material of the present invention, the target to use the generated hydrogen (hydrogen supply destination) may be a target to supply hydrogen by directly or indirectly contacting the material of the present invention. In particular, those capable of maintaining or improving physical properties by the action of hydrogen (for example, reduction action) are preferred. The hydrogen supply destination may be water or a liquid containing water, or a solid or gas containing water. Further, the hydrogen supply destination may be pure water, an aqueous solution, an aqueous dispersion, or the like. Therefore, for example, a) foods such as beverages, meats, seafood, vegetables, fruits, etc. b) processed foods made from the above ingredients, as well as fresh flowers, fungi, bacteria, plant seeds, blood for transfusion, infusion Examples of the hydrogen supply destination include bath water, washing water, detergent, air, wound dressing material, cosmetics, diapers, pet beverages, breeding aquarium water, microorganisms, soil, food, indoor space, human body, animals and plants. These can be a water supply source and a water supply source for the hydrogen generating material, but the water supply source and the hydrogen supply destination may be different. In particular, the hydrogen supply destination is preferably a moisture supply source for the hydrogen generating material.
以下においては、本発明の水素発生材料を構成する成分等について、より具体的に説明する。 Below, the component etc. which comprise the hydrogen generating material of this invention are demonstrated more concretely.
（１）水素発生粒子
水素発生粒子は、水と接触することによって水素（水素ガス）を発生するものであれば良い。水は、液体の水のほか、水蒸気でも良い。また、水は、純水のほか、水溶液、水分散液等のいずれでも良い。
(1) Hydrogen generating particles The hydrogen generating particles may be anything that generates hydrogen (hydrogen gas) by contact with water. The water may be liquid water or water vapor. The water may be pure water, an aqueous solution, an aqueous dispersion, or the like.
水素発生粒子は、水素発生可能であればその種類は限定されない。例えば、水素化マグネシウム、水素化カルシウム、水素化バリウム、水素化ベリリウム、水素化ストロンチウム、水素化リチウム、水素化ナトリウム、水素化ホウ素ナトリウム、水素化リチウムナトリウム、水素化ケイ素等の水素化金属粒子のほか、マグネシウム、アルミニウム等の金属単体又はそれらを含む合金が挙げられる。これらは、１種又は２種以上で用いることができる。 The type of hydrogen generating particles is not limited as long as hydrogen generation is possible. For example, metal hydride particles such as magnesium hydride, calcium hydride, barium hydride, beryllium hydride, strontium hydride, lithium hydride, sodium hydride, sodium borohydride, lithium sodium hydride, silicon hydride, etc. In addition, a simple metal such as magnesium or aluminum or an alloy containing them can be used. These can be used alone or in combination of two or more.
水素発生粒子の大きさは、特に限定されないが、例えば体積平均粒子径が１〜１００μｍであることが好ましい。体積平均粒子径が１μｍ未満の場合は水素発生粒子どうしが凝集しやすくなり、マトリックス用樹脂への分散性が低下することがある。また、１００μｍを超えると水素発生粒子が重くなるため、マトリックス用樹脂への分散性が低くなるおそれがある。ここで、水素発生粒子の体積平均粒子径とは、レーザー回折法により測定された水素発生粒子群の体積累積粒度分布の結果から平均粒径Ｄ５０（５０％粒子径）を算出した値である。 The size of the hydrogen generating particles is not particularly limited, but for example, the volume average particle diameter is preferably 1 to 100 μm. When the volume average particle diameter is less than 1 μm, the hydrogen generating particles tend to aggregate and the dispersibility in the matrix resin may be reduced. On the other hand, when the thickness exceeds 100 μm, the hydrogen generating particles become heavy, so that the dispersibility in the matrix resin may be lowered. Here, the volume average particle diameter of the hydrogen generating particles is a value obtained by calculating the average particle diameter D50 (50% particle diameter) from the result of the volume cumulative particle size distribution of the hydrogen generating particle group measured by the laser diffraction method.
（２）被覆用樹脂
被覆用樹脂は、少なくとも本発明材料表面から突出した水素発生粒子の表面を被覆するための樹脂である。図５で例示したように、本発明材料表面１０ａから突出した水素発生粒子３０の表面を被覆用樹脂を含む被覆層２０で覆うことにより、水素発生粒子が外部に直接露出しない状態とする。この場合、水素発生粒子３０における本発明材料表面１０ａより下方の領域は、被覆層２０で覆われていても良いし、覆われていなくても良い。さらに、本発明材料中に完全に埋まっている水素発生粒子については、その全体が被覆層で覆われていなくても良いし、被覆層で覆われていても良い。
(2) Coating resin The coating resin is a resin for coating at least the surface of the hydrogen generating particles protruding from the surface of the material of the present invention. As illustrated in FIG. 5, the surface of the hydrogen generating particles 30 protruding from the material surface 10a of the present invention is covered with the coating layer 20 containing the coating resin, so that the hydrogen generating particles are not directly exposed to the outside. In this case, the region below the surface 10a of the present invention material in the hydrogen generating particle 30 may be covered with the coating layer 20 or may not be covered. Further, the hydrogen generating particles completely embedded in the material of the present invention may not be entirely covered with the coating layer, or may be covered with the coating layer.
被覆層の厚みは、特に限定されないが、通常は１ｎｍ〜５０μｍ程度の範囲内で適宜設定することが好ましい。厚みが１ｎｍ未満である場合は、各種水素発生粒子を構成する成分が水に溶出するおそれがある。また、厚みが５０μｍを超えると十分な水素発生量が得られないおそれがある。 Although the thickness of a coating layer is not specifically limited, Usually, it is preferable to set suitably in the range of about 1 nm-50 micrometers. When the thickness is less than 1 nm, components constituting various hydrogen generating particles may be eluted in water. On the other hand, if the thickness exceeds 50 μm, a sufficient hydrogen generation amount may not be obtained.
被覆用樹脂の種類は、特に限定されないが、特にポリオレフィン樹脂及びポリアミド樹脂の少なくとも１種を好適に採用することができる。ポリオレフィン樹脂としては、例えばポリエチレン、ポリプロピレン等を好適に採用することができる。 Although the kind of resin for coating | cover is not specifically limited, At least 1 sort (s) of polyolefin resin and polyamide resin can be employ | adopted suitably especially. As the polyolefin resin, for example, polyethylene, polypropylene, or the like can be suitably employed.
（３）マトリックス用樹脂
マトリックス用樹脂は、水素発生粒子が分散されるマトリックスを構成する樹脂（ポリマー）である。すなわち、マトリックス用樹脂によって水素発生粒子が支持・固定されることになる。
(3) Matrix Resin The matrix resin is a resin (polymer) that constitutes a matrix in which hydrogen generating particles are dispersed. That is, the hydrogen generating particles are supported and fixed by the matrix resin.
マトリックス用樹脂は、水素発生粒子を本発明材料中で固定できる限り、特に限定されない。また、本発明の効果を妨げない限りにおいて、マトリックス用樹脂は、固体（例えばフィルム状等）であっても良いし、流動性を有する性状であっても良い。例えばマトリックス用樹脂が固体である場合は、例えばポリエチレン、ポリプロピレン等のポリオレフィン樹脂、スチロール樹脂、塩化ビニル樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ポリアミド樹脂、ポリエチレングリコール、ポリエチレンオキサイド等の少なくとも１種を採用することができる。また、マトリックス用樹脂がコート状である場合には、例えばウレタン樹脂、フッ素樹脂、変性フッ素樹脂、ポリオレフィン樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、塩化ビニル樹脂、ポリエチレングリコール、ポリエチレンオキサイド等の少なくとも１種を用いることができる。マトリックス用樹脂がコート状である場合には、必要に応じて、上記樹脂以外にも溶剤等を配合して使用しても良い。特に、マトリックス用樹脂がポリエチレンである場合は、表面に被覆層を備える水素発生粒子の分散性がより良好となるので好ましい。 The matrix resin is not particularly limited as long as the hydrogen generating particles can be fixed in the material of the present invention. As long as the effects of the present invention are not hindered, the matrix resin may be solid (for example, a film) or may have fluidity. For example, when the matrix resin is solid, at least one of a polyolefin resin such as polyethylene and polypropylene, a polyester resin such as styrene resin, vinyl chloride resin and polyethylene terephthalate, a polyamide resin, polyethylene glycol, and polyethylene oxide is employed. be able to. When the matrix resin is in the form of a coat, for example, at least one of urethane resin, fluororesin, modified fluororesin, polyolefin resin, epoxy resin, polyester resin, polyamide resin, vinyl chloride resin, polyethylene glycol, polyethylene oxide, etc. Seeds can be used. When the matrix resin is in the form of a coat, if necessary, a solvent or the like may be blended in addition to the resin. In particular, when the matrix resin is polyethylene, the dispersibility of the hydrogen generating particles having a coating layer on the surface becomes better, which is preferable.
また、マトリックス用樹脂は、被覆用樹脂と同じ成分（組成）であっても良いし、異なっていても良い。ただし、マトリックス用樹脂と被覆用樹脂とが互いに同じであれば、より高い密着性が得られる。その結果、水素発生粒子の脱落をより効果的に抑制することができる。一方、マトリックス用樹脂と被覆用樹脂とが互いに異なる場合には、例えば水分の透過速度を制御することができ、水素発生量を制御することができる。こうした水素発生量の制御は、マトリックス用樹脂と被覆用樹脂とが同じであっても、それぞれの密度等を変えることで制御することができる。 The matrix resin may be the same component (composition) as the coating resin or may be different. However, if the matrix resin and the coating resin are the same, higher adhesion can be obtained. As a result, falling off of the hydrogen generating particles can be more effectively suppressed. On the other hand, when the matrix resin and the coating resin are different from each other, for example, the moisture permeation rate can be controlled, and the amount of hydrogen generation can be controlled. Such control of the amount of hydrogen generation can be controlled by changing the density and the like of the matrix resin and the coating resin even if they are the same.
本発明材料がフィルム状である場合、その厚み（すなわち、マトリックス用樹脂層の厚さ）は、限定されないが、例えば１０〜１５０μｍの範囲であると、より好適に水素供給先へ過不足なく効率的に水素を供給することができる。 When the material of the present invention is in the form of a film, the thickness (that is, the thickness of the resin layer for the matrix) is not limited. Hydrogen can be supplied.
２．水素発生材料の使用
本発明材料は、その用途、使用目的等に応じた形態で各種の製品に適用することができる。また、必要に応じて、本発明材料をフィルム状の形態としたうえで使用することができるほか、そのフィルムの少なくとも一方の面に他の層を積層してなる積層体の形態で使用することもできる。他の層としては、例えば紙、金属缶、金属板、金属箔、金属蒸着膜、不織布、布、樹脂からなる群から選択される一種又は２種以上の層が挙げられる。
2. Use of Hydrogen Generating Material The material of the present invention can be applied to various products in a form corresponding to its use, purpose of use and the like. If necessary, the material of the present invention can be used in the form of a film and used in the form of a laminate in which another layer is laminated on at least one surface of the film. You can also. Examples of the other layer include one or two or more layers selected from the group consisting of paper, metal can, metal plate, metal foil, metal vapor-deposited film, nonwoven fabric, cloth, and resin.
また、本発明材料は、特に本発明材料表面が水素供給先となる対象（特に水又は水を含む材料）に直に接するように配置することが望ましい。例えば、本発明材料を用いて水素発生容器を構成する場合は、容器の最も内面側に本発明材料が配置されるようにすれば良い。また、水素供給先に貼着して使用する場合は、例えばその水素供給先となる対象（物品）に直に接するように本発明材料を貼り付ければ良い。これにより、本発明材料表面から発生した水素を水素供給先に供給することができる。 In addition, it is desirable that the material of the present invention be disposed so that the surface of the material of the present invention is in direct contact with the target (particularly water or water-containing material) as the hydrogen supply destination. For example, when a hydrogen generation container is configured using the material of the present invention, the material of the present invention may be arranged on the innermost surface side of the container. Moreover, when sticking to a hydrogen supply destination and using it, what is necessary is just to stick this invention material so that the object (article) used as the hydrogen supply destination may touch directly. Thereby, hydrogen generated from the surface of the material of the present invention can be supplied to the hydrogen supply destination.
３．水素発生材料の製造方法
本発明の水素発生材料は、例えば以下の製造方法によって好適に得ることができる。すなわち、水と接触することにより水素を発生する材料を製造する方法であって、
（１）ａ）水と反応して水素を発生し得る水素発生粒子及びｂ）被覆用樹脂とを含む混合物を調製する工程（第１工程）、
（２）前記混合物をマトリックス用樹脂と混合する工程（第２工程）
を含むことを特徴とする製造方法により、本発明材料を好適に製造することができる。特に、上記の製造方法により得られる本発明材料を好適に用いることができる。
3. Method for Producing Hydrogen Generating Material The hydrogen generating material of the present invention can be suitably obtained by the following production method, for example. That is, a method for producing a material that generates hydrogen by contact with water,
(1) a) a step (first step) of preparing a mixture containing hydrogen generating particles capable of generating hydrogen by reacting with water and b) a coating resin;
(2) Step of mixing the mixture with a matrix resin (second step)
The material of the present invention can be preferably produced by a production method comprising In particular, the material of the present invention obtained by the above production method can be suitably used.
第１工程
第１工程では、ａ）水と反応して水素を発生し得る水素発生粒子及びｂ）被覆用樹脂とを含む混合物を調製する。
First Step In the first step, a mixture containing a) hydrogen generating particles capable of generating hydrogen by reacting with water and b) a coating resin is prepared.
混合物の形態としては、例えば水素発生粒子の複数個が被覆用樹脂中に含まれるコンパウンドの形態（例えば図４の粒子Ａ）、１つの水素発生粒子の表面が被覆用樹脂で覆われた被覆粒子の形態等のいずれの形態であっても良い。本発明では、特にことわりのない限り、これら混合物を総称して「複合粒子」という。 As the form of the mixture, for example, a compound form in which a plurality of hydrogen generating particles are contained in the coating resin (for example, particle A in FIG. 4), a coated particle in which the surface of one hydrogen generating particle is covered with the coating resin. It may be any form such as. In the present invention, unless otherwise specified, these mixtures are collectively referred to as “composite particles”.
従って、第１工程では、その複合粒子の形態に応じて実施する方法を選択すれば良い。この場合、例えば水素発生粒子の種類、被覆用樹脂の種類及び配合量等は、前記「１．水素発生材料」で説明した内容に従えば良い。 Therefore, what is necessary is just to select the method implemented according to the form of the composite particle in a 1st process. In this case, for example, the type of the hydrogen generating particles, the type and the amount of the coating resin, etc. may be in accordance with the contents described in “1.
混合物として、コンパウンドを調製する場合は、例えばi)水素発生粒子と溶融した被覆用樹脂とを混練する方法、ii)溶融した被覆用樹脂と水素発生粒子とを含む混合物を噴射する方法等を採用することができる。 When preparing a compound as a mixture, for example, i) a method of kneading hydrogen generating particles and molten coating resin, ii) a method of injecting a mixture containing molten coating resin and hydrogen generating particles, etc. can do.
混合物として、１つの水素発生粒子の表面が被覆用樹脂で覆われた被覆粒子を調製する場合は、例えば水素発生粒子を攪拌するとともにスプレーコートにより被覆用樹脂を吹き付けてコートする方法等を採用することができる。 When preparing coated particles in which the surface of one hydrogen generating particle is covered with a coating resin as a mixture, for example, a method of stirring the hydrogen generating particles and spraying the coating resin by spray coating is used. be able to.
第２工程
第２工程では、前記混合物をマトリックス用樹脂と混合する。これにより、マトリックス中に水素発生粒子が分散するとともに、得られる水素発生材料表面から突出する水素発生粒子の表面が被覆用樹脂を含む被覆層で覆われた構造を形成することができる。
Second Step In the second step, the mixture is mixed with a matrix resin. As a result, it is possible to form a structure in which the hydrogen generating particles are dispersed in the matrix and the surface of the hydrogen generating particles protruding from the surface of the obtained hydrogen generating material is covered with the coating layer containing the coating resin.
混合する方法は、特に限定されないが、例えばi)複合粒子又はコンパウンドを液状マトリックス用樹脂（溶融樹脂）に混合攪拌する方法、ii)水素発生粒子と被覆用樹脂との混練物をマトリックス用樹脂と共押し出しすることにより、水素発生粒子と被覆用樹脂がエマルジョンの様な状態となって水素発生粒子の表面に被覆用樹脂が被覆した状態でマトリックス用樹脂中に分散したフィルムを製膜する方法、iii)溶融したマトリックス用樹脂に複合粒子を塗布又は散布する方法等を採用することができる。また、水素発生粒子と被覆用樹脂がエマルジョンの様な状態となってマトリックス用樹脂中に分散する場合には、第１工程と第２工程とを実質的に同時に行うことができる。 The mixing method is not particularly limited. For example, i) a method in which composite particles or compounds are mixed and stirred in a liquid matrix resin (molten resin), and ii) a kneaded product of hydrogen generating particles and a coating resin is used as a matrix resin. A method of forming a film dispersed in a matrix resin in a state where the hydrogen generating particles and the coating resin are in an emulsion-like state and the coating resin is coated on the surface of the hydrogen generating particles by coextrusion; iii) A method of applying or dispersing the composite particles on the molten matrix resin can be employed. Further, when the hydrogen generating particles and the coating resin are in an emulsion-like state and dispersed in the matrix resin, the first step and the second step can be performed substantially simultaneously.
なお、上記のように第２工程では、成形も同時に実施しても良いが、第２工程で得られた水素発生材料をさらに成形工程を供することもできる。成形方法としては、公知の樹脂組成物を成形する場合に採用されている方法と同様にすれば良い。 As described above, in the second step, molding may be performed at the same time, but the hydrogen generating material obtained in the second step can be further subjected to a molding step. The molding method may be the same as the method adopted when molding a known resin composition.
以下に実施例及び比較例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.
実施例１
水素発生粒子となる市販の水素化マグネシウム粉末（和光純薬工業株式会社 体積平均粒子径Ｄ５０＝１５μｍ）を被覆用樹脂となる市販のポリエチレン樹脂に練り込み、水素化マグネシウム含有コンパウンド（粒径約３ｍｍ）を作製した。その割合は、ポリエチレン樹脂全量に対して水素化マグネシウム粉末５重量％とした。
水素化マグネシウム含有コンパウンド１重量部とマトリックス用樹脂となる市販のペレット状ポリエチレン樹脂４重量部とを十分に混合した状態で溶融押出成形法によりフィルム状（厚み約１００μｍ）に製膜した。このとき、マトリックス用樹脂に対する水素発生粒子は１重量％とした。これにより、図１に示すように、被覆用ポリエチレン樹脂２０により被覆された水素化マグネシウム粒子３０がマトリックス用ポリエチレン樹脂１０に分散した水素発生材料１を得た。
Example 1
Commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd., volume average particle diameter D50 = 15 μm) serving as hydrogen generating particles is kneaded into a commercially available polyethylene resin serving as a coating resin, and a magnesium hydride-containing compound (particle size of about 3 mm) ) Was produced. The proportion was 5% by weight of magnesium hydride powder with respect to the total amount of polyethylene resin.
A film (thickness: about 100 μm) was formed by melt extrusion molding in a state in which 1 part by weight of a magnesium hydride-containing compound and 4 parts by weight of a commercially available pellet-like polyethylene resin serving as a matrix resin were sufficiently mixed. At this time, the hydrogen generation particles with respect to the matrix resin were 1% by weight. Thereby, as shown in FIG. 1, the hydrogen generating material 1 in which the magnesium hydride particles 30 coated with the coating polyethylene resin 20 were dispersed in the matrix polyethylene resin 10 was obtained.
実施例２
マトリックス用樹脂に対する水素発生粒子を０．３重量％とした以外は、実施例１と同様にして水素発生材料を製造した。
Example 2
A hydrogen generating material was produced in the same manner as in Example 1 except that the amount of hydrogen generating particles relative to the matrix resin was 0.3% by weight.
実施例３
マトリックス用樹脂に対する水素発生粒子を５重量％とした以外は、実施例１と同様にして水素発生材料を製造した。
Example 3
A hydrogen generating material was produced in the same manner as in Example 1 except that the amount of hydrogen generating particles relative to the matrix resin was changed to 5% by weight.
実施例４
水素発生粒子として市販のアルミニウム粉末（東洋アルミニウム株式会社１Ｎ３０、体積平均粒子径Ｄ５０＝１０μｍ）を用いたほかは、実施例１と同様にして水素発生材料を製造した。
Example 4
A hydrogen generating material was produced in the same manner as in Example 1 except that a commercially available aluminum powder (Toyo Aluminum Co., Ltd. 1N30, volume average particle diameter D50 = 10 μm) was used as the hydrogen generating particles.
比較例１
被覆用樹脂を用いずに、マトリックス用樹脂９９重量部に市販の水素化マグネシウム粉末（和光純薬工業株式会社 体積平均粒子径Ｄ５０＝１５μｍ）１重量部を直接投入して溶融押出成形法によりフィルム状に製膜し、図２に示すような１層の樹脂層１２中に水素発生粒子３２を分散して樹脂層１２の表面に一部の水素発生粒子３２が外部に直に露出（露呈）するような構成の水素発生材料を得た。
Comparative Example 1
Without using a resin for coating, 1 part by weight of commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd., volume average particle diameter D50 = 15 μm) is directly added to 99 parts by weight of matrix resin, and a film is obtained by melt extrusion molding. The hydrogen generating particles 32 are dispersed in one resin layer 12 as shown in FIG. 2, and a part of the hydrogen generating particles 32 are directly exposed to the surface of the resin layer 12 (exposed). A hydrogen generating material having such a structure was obtained.
比較例２
比較例１と同様にしてマトリックス用樹脂９９重量部中に市販の水素化マグネシウム粉末（和光純薬工業株式会社 体積平均粒子径Ｄ５０＝１５μｍ）１重量部を直接投入して溶融押出成形法によりフィルム状に製膜し、さらにこのフィルムの表面に厚さ５０μｍのポリエチレンフィルム（タマポリ社製ＬＣ−２Ｔ）を積層して、図３に示すような１層の樹脂層１４中に水素発生粒子３４を分散して、樹脂層１４の表面に樹脂層２４を積層した水素発生材料を得た。
Comparative Example 2
As in Comparative Example 1, 1 part by weight of commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd., volume average particle diameter D50 = 15 μm) was directly charged into 99 parts by weight of the matrix resin, and a film was obtained by melt extrusion molding. Further, a 50 μm thick polyethylene film (LC-2T manufactured by Tamapoly Co., Ltd.) is laminated on the surface of this film, and hydrogen generating particles 34 are placed in one resin layer 14 as shown in FIG. Dispersed to obtain a hydrogen generating material in which the resin layer 24 was laminated on the surface of the resin layer 14.
試験例１
各実施例及び比較例で得られた水素発生材料を、共栓三角フラスコ内で純水（２０℃）に２４時間浸漬させ、水中の水素濃度（溶存水素濃度）と水素発生粒子の金属成分であるマグネシウムイオン濃度とをそれぞれ測定した。なお、共栓三角フラスコは栓にガラス管が貫通して取り付けられ、ガラス管の一端はフラスコ内の底部付近まで延びてフラスコ内の内圧を逃す構造とした。
水素濃度の測定については、ユニセンス社製「Ｈ２−５００ｓｅｎｓｏｒ」を使用した。水素濃度が０．１ｍｇ／Ｌ以上である場合を「○」とし、これ未満を「×」とした。
また、マグネシウムイオン濃度の測定については、株式会社島津製作所製ＩＣＰ発光分析装置（型式ＩＣＰＳ−８１００）を用いて測定した。水中のマグネシウムイオン濃度が１ｍｇ／Ｌ未満の場合を「○」とし、これ以上のものを「×」とした。これらの結果を表１に示す。
Test example 1
The hydrogen generating material obtained in each Example and Comparative Example was immersed in pure water (20 ° C.) for 24 hours in a stoppered Erlenmeyer flask, and the hydrogen concentration in water (dissolved hydrogen concentration) and the metal components of the hydrogen generating particles Each magnesium ion concentration was measured. The stoppered Erlenmeyer flask has a structure in which a glass tube passes through the stopper and one end of the glass tube extends to the vicinity of the bottom in the flask to release the internal pressure in the flask.
For the measurement of the hydrogen concentration, “H2-500 sensor” manufactured by Unisense was used. The case where the hydrogen concentration was 0.1 mg / L or more was designated as “◯”, and the case where the hydrogen concentration was less than this was designated as “x”.
The magnesium ion concentration was measured using an ICP emission spectrometer (model ICPS-8100) manufactured by Shimadzu Corporation. The case where the magnesium ion concentration in water was less than 1 mg / L was designated as “◯”, and the case where the magnesium ion concentration was higher than that was designated as “x”. These results are shown in Table 1.
表１の結果からも明らかなように、本発明の水素発生材料は、水素供給先と水素発生層との間に必ずしも介在層を有する必要がなく、水素供給先に水素を安全に供給できることがわかる。 As is clear from the results in Table 1, the hydrogen generating material of the present invention does not necessarily have an intervening layer between the hydrogen supply destination and the hydrogen generation layer, and can supply hydrogen safely to the hydrogen supply destination. Recognize.
Claims (7)
（１）ａ）水と反応して水素を発生し得る水素発生粒子、ｂ）被覆用樹脂及びｃ）マトリックス用樹脂を含み、
（２）少なくとも当該材料表面から突出する水素発生粒子の表面が被覆用樹脂を含む被覆層で覆われている、
ことを特徴とする水素発生材料。 A material that generates hydrogen by contact with water,
(1) a) hydrogen generating particles capable of generating hydrogen by reacting with water, b) a coating resin and c) a matrix resin,
(2) At least the surface of the hydrogen generating particles protruding from the material surface is covered with a coating layer containing a coating resin.
A hydrogen generating material characterized by that.
（１）ａ）水と反応して水素を発生し得る水素発生粒子及びｂ）被覆用樹脂とを含む混合物を調製する工程、
（２）前記混合物をマトリックス用樹脂と混合する工程
を含むことを特徴とする水素発生材料の製造方法。 A method for producing a material that generates hydrogen by contact with water,
(1) a) preparing a mixture containing hydrogen generating particles capable of generating hydrogen by reacting with water and b) a coating resin;
(2) A method for producing a hydrogen generating material, comprising a step of mixing the mixture with a matrix resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018074253A JP7096049B2 (en) | 2018-04-06 | 2018-04-06 | Hydrogen generating material and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018074253A JP7096049B2 (en) | 2018-04-06 | 2018-04-06 | Hydrogen generating material and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019182699A true JP2019182699A (en) | 2019-10-24 |
| JP7096049B2 JP7096049B2 (en) | 2022-07-05 |
Family
ID=68339465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018074253A Active JP7096049B2 (en) | 2018-04-06 | 2018-04-06 | Hydrogen generating material and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7096049B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314793A (en) * | 2022-01-06 | 2022-04-12 | 青岛诺康新氢源研究院有限公司 | Hydrogen production particle capable of generating porous structure on site and preparation method and application thereof |
| WO2022163376A1 (en) * | 2021-01-29 | 2022-08-04 | バイオコーク技研株式会社 | Hydrogen generation sheet, swaddle, packaging material, and method of manufacturing hydrogen generation sheet |
| WO2024043197A1 (en) * | 2022-08-22 | 2024-02-29 | 東洋アルミニウム株式会社 | Hydrogen generator |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008132986A1 (en) * | 2007-04-12 | 2008-11-06 | Hiromaito Co., Ltd. | Hydrogen-generating agent, method for production thereof, and hydrogen generation apparatus |
| JP2013184833A (en) * | 2012-03-06 | 2013-09-19 | Kracie Home Products Ltd | Molding |
| JP2013537500A (en) * | 2010-07-06 | 2013-10-03 | ラ セダ デ バルセロナ ソシエダ アノニマ | Suitable seal for generating molecular hydrogen and closing the container to scavenge oxygen |
| JP2014104455A (en) * | 2012-11-30 | 2014-06-09 | Hiroshi Ota | Vessel having hydrogen generating function, and hydrogen addition method |
| WO2015093184A1 (en) * | 2013-12-16 | 2015-06-25 | 皓士 大田 | Hydrogen-generating agent and hydrogen generation method |
| JP2018003197A (en) * | 2016-07-01 | 2018-01-11 | 皓士 大田 | Fabric with hydrogen generating function and method for manufacturing the same |
-
2018
- 2018-04-06 JP JP2018074253A patent/JP7096049B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008132986A1 (en) * | 2007-04-12 | 2008-11-06 | Hiromaito Co., Ltd. | Hydrogen-generating agent, method for production thereof, and hydrogen generation apparatus |
| JP2013537500A (en) * | 2010-07-06 | 2013-10-03 | ラ セダ デ バルセロナ ソシエダ アノニマ | Suitable seal for generating molecular hydrogen and closing the container to scavenge oxygen |
| JP2013184833A (en) * | 2012-03-06 | 2013-09-19 | Kracie Home Products Ltd | Molding |
| JP2014104455A (en) * | 2012-11-30 | 2014-06-09 | Hiroshi Ota | Vessel having hydrogen generating function, and hydrogen addition method |
| WO2015093184A1 (en) * | 2013-12-16 | 2015-06-25 | 皓士 大田 | Hydrogen-generating agent and hydrogen generation method |
| JP2018003197A (en) * | 2016-07-01 | 2018-01-11 | 皓士 大田 | Fabric with hydrogen generating function and method for manufacturing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022163376A1 (en) * | 2021-01-29 | 2022-08-04 | バイオコーク技研株式会社 | Hydrogen generation sheet, swaddle, packaging material, and method of manufacturing hydrogen generation sheet |
| CN114314793A (en) * | 2022-01-06 | 2022-04-12 | 青岛诺康新氢源研究院有限公司 | Hydrogen production particle capable of generating porous structure on site and preparation method and application thereof |
| WO2024043197A1 (en) * | 2022-08-22 | 2024-02-29 | 東洋アルミニウム株式会社 | Hydrogen generator |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7096049B2 (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2019182699A (en) | Hydrogen generating material and manufacturing method therefor | |
| CN100349794C (en) | Energy-activated compositions for controlled sustained release of gas | |
| KR102114024B1 (en) | Adhesive for packaging materials, and packaging material | |
| US9403160B2 (en) | Method for producing micro-nano combined active systems | |
| US20100047546A1 (en) | Non-Metallic Nano/Micro Particles Coated with Metal, Process and Applications Thereof | |
| EP3438055B1 (en) | Ferrite powder, resin composition, and molded article | |
| CN109562609A (en) | Oxygen-barrier property plastic material | |
| JPWO2017169036A1 (en) | Oxygen absorbent composition, oxygen-absorbing multilayer body, oxygen-absorbing packaging container, and article storage method | |
| JPH11263705A (en) | Antimicrobial and antimicrobial resin composition | |
| KR101813208B1 (en) | Manufacturing Method of Antibacterial Packing Material for Keeping Freshness of Food | |
| KR101796074B1 (en) | Bioplastic with improved insect-proof and antimicrobial and a method there of | |
| CN111867376A (en) | Antimicrobial coating material comprising nanocrystalline cellulose and magnesium oxide and method of making the same | |
| MX2013013413A (en) | Shaped bodies having antibacterial action, method for sterilizing formulations, storage container containing said shaped bodies, and use of the storage container. | |
| JP2006069935A (en) | Material for forming silver ion water and method for producing silver ion water by using the same | |
| TW201806872A (en) | Ferrite powder, resin composition, and molded article | |
| JPWO2014021430A1 (en) | Method for producing oxygen absorbent | |
| JP2014012752A (en) | Multifunctional resin inclusion paper composition | |
| JP6674032B2 (en) | Manufacturing method of antibacterial container | |
| JP2023064370A (en) | Hydrogen generating material and manufacturing method thereof | |
| JPH0680528A (en) | Antimicrobial phosphate double salt, its propellant and its use | |
| KR101850629B1 (en) | Composition comprising nanostructure layered double hydroxide with antimicrobial agent for shelf-life extension of fresh-cut produce | |
| CN101195477A (en) | Energy-activated compositions for controlled sustained release of a gas | |
| JP2016008201A (en) | Smoking agent | |
| JP6819849B2 (en) | Oxygen absorption molded article and its manufacturing method, oxygen absorption multilayer body, and oxygen absorption package | |
| JP2012036282A (en) | Silver-containing resin composition, and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210315 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220228 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220308 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220427 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220621 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220623 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7096049 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |