JPH0532328B2 - - Google Patents
Info
- Publication number
- JPH0532328B2 JPH0532328B2 JP3047385A JP3047385A JPH0532328B2 JP H0532328 B2 JPH0532328 B2 JP H0532328B2 JP 3047385 A JP3047385 A JP 3047385A JP 3047385 A JP3047385 A JP 3047385A JP H0532328 B2 JPH0532328 B2 JP H0532328B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- alkaline earth
- aqueous solution
- silver nitrate
- weight
- 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.)
- Expired - Lifetime
Links
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 50
- 239000004332 silver Substances 0.000 claims description 46
- 229910052709 silver Inorganic materials 0.000 claims description 46
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 44
- 239000004579 marble Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AVTYONGGKAJVTE-UHFFFAOYSA-L potassium tartrate Chemical class [K+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O AVTYONGGKAJVTE-UHFFFAOYSA-L 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- XHXKMTAWMZESFU-UHFFFAOYSA-M silver;hydrogen carbonate Chemical compound [Ag+].OC([O-])=O XHXKMTAWMZESFU-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Chemically Coating (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、炭酸カルシウム、炭酸マグネシウム
等のアルカリ土類金属の炭酸塩、又はアルカリ土
類金属の酸化物固体表面に銀をコーテイングする
方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for coating a solid surface of an alkaline earth metal carbonate such as calcium carbonate or magnesium carbonate or an alkaline earth metal oxide with silver. It is something.
〔従来技術及びその問題点〕
従来の銀コーテイング法としては、硝酸銀水溶
液に過剰のアンモニア水を加えてアンモニア性硝
酸銀錯塩を生成し、これにアルデヒド等の還元剤
を加えた溶液を用いて、ガラス、銅、鉄等のの固
体表面に金属銀を析出させる方法が良く知られて
いる。[Prior art and its problems] In the conventional silver coating method, an ammoniacal silver nitrate complex is produced by adding excess aqueous ammonia to an aqueous solution of silver nitrate, and a reducing agent such as an aldehyde is added to this solution. A well-known method is to deposit metallic silver on the solid surface of copper, iron, etc.
また、同様な方法により活性炭或いはコーラル
サンド上に銀を析出せしめたものを水の殺菌剤と
して使用することも知られている（特開昭51−
90996号公報、実開昭58−86297号公報）。 It is also known that silver is precipitated on activated carbon or coral sand using a similar method and used as a water disinfectant (Japanese Patent Laid-Open No. 1983-1999).
90996, Utility Model Application Publication No. 1986-86297).
ところで、アンモニア性硝酸銀水溶液を用いて
銀を固体表面に析出させる場合、銀はあらゆる固
体表面上に析出するため、該反応を行わせる容器
上にも析出し、銀が無駄に消費されるという欠点
があつた。 By the way, when silver is deposited on a solid surface using an ammoniacal silver nitrate aqueous solution, since silver is deposited on every solid surface, it is also deposited on the container in which the reaction is carried out, resulting in a disadvantage that silver is wasted. It was hot.
本発明は、アンモニアを使用することなく、酸
性を示す還元剤と0.5〜10重量％の硝酸銀水溶液
を混合してPHを１〜５に調整した溶液を用いてア
ルカリ土類金属の炭酸塩又は酸化物又はこれらの
混合物よりなる固形物表面に銀コーテイングを行
うことにより、容器壁への銀の付着等による銀の
損失を防止し、効率的に銀コーテイングを行う方
法を提供することを目的とするものである。
The present invention produces alkaline earth metal carbonates or oxidizers using a solution prepared by mixing an acidic reducing agent and a 0.5 to 10% by weight silver nitrate aqueous solution to adjust the pH to 1 to 5, without using ammonia. The purpose of this invention is to provide a method for efficiently coating silver by coating the surface of a solid substance made of a substance or a mixture thereof, thereby preventing loss of silver due to adhesion of silver to the container wall, etc. It is something.
本発明は、酸性を示す還元剤と、0.5〜10重量
％の硝酸銀水溶液を混合してPHを１〜５に調整し
た溶液を用いてアルカリ土類金属の炭酸塩又は酸
化物又はこれらの混合物を処理することを特徴と
する該化合物よりなる固形物表面に銀をコーテイ
ングする方法である。
In the present invention, carbonates or oxides of alkaline earth metals, or mixtures thereof, are prepared by mixing an acidic reducing agent and a 0.5 to 10% by weight silver nitrate aqueous solution to adjust the pH to 1 to 5. This is a method of coating the surface of a solid material made of the compound with silver.
更に詳しく説明すると、本発明は、硝酸銀溶液
にヒドロキシカルボン酸を加えてPH１〜５の酸性
を保持しつつ、アルカリ土類金属炭酸塩又は酸化
物を浸せきし、これら固形物の塩基性表面に銀を
析出させることを特徴としたものである。 To explain in more detail, the present invention involves adding hydroxycarboxylic acid to a silver nitrate solution to maintain acidity of pH 1 to 5, and dipping alkaline earth metal carbonates or oxides into the silver nitrate solution to coat the basic surface of these solids with silver. It is characterized by precipitating.
本発明において銀コーテイングする対象物は、
炭酸カルシウム、炭酸マグネシウム等のアルカリ
土類金属炭酸塩又は酸化物を主成分とする固形物
に限定される。 The objects to be coated with silver in the present invention are:
It is limited to solid substances whose main components are alkaline earth metal carbonates or oxides such as calcium carbonate and magnesium carbonate.
この場合通常使用されるアンモニア水は必要と
しない。 In this case, the normally used ammonia water is not required.
本発明ではヒドロキシカルボン酸を還元剤とし
て使用しアンモニア水を使用しないで直接硝酸銀
溶液から金属銀を析出させるが、このような方法
については、従来何ら文献報告はみられない。わ
ずかにロツシエル塩（酒石酸のナトリウム及びカ
リウム塩）と硝酸銀の反応による方法〔(1)ウルマ
ン著：エンシクロペデイエ デルテヒニツシエン
ヘミー、第２巻 第５号775頁（Ullmann：
Enzyklopａ¨die der Technischen Chemie，
2Aufl.5 775），(2)イシドア クロス著，メタル
フイニツシング，第48巻 第12号 77頁（1950
年）（Isidore Cross，Metal Finishing，48（12）
77（1950）〕が述べられているに過ぎない。 In the present invention, metallic silver is directly precipitated from a silver nitrate solution using a hydroxycarboxylic acid as a reducing agent without using aqueous ammonia, but there have been no prior literature reports regarding such a method. A method based on the reaction of slightly Rothsiel's salts (sodium and potassium tartaric acid salts) and silver nitrate [(1) Ullmann: Encyclopédie Dertechnischen Chemie, Vol. 2, No. 5, p. 775 (Ullmann:
Enzyklopa¨die der Technischen Chemie,
2Aufl.5 775), (2) Isidore Cross, Metal
Finishing, Vol. 48, No. 12, p. 77 (1950)
) (Isidore Cross, Metal Finishing, 48(12)
77 (1950)].
担体が塩基性を示さない物質では参考例１に示
すようにヒドロキシカルボン酸の酸性溶液中にお
いて銀の還元反応は進行しない。従つて、本発明
ではヒドロキシカルボン酸と硝酸銀が、アルカリ
土類金属炭酸塩又は酸化物の固体表面の塩基性の
作用によりヒドロキシカルボン酸銀を生成し、こ
れが生成するアルデヒドによつて還元され、アル
カリ土類金属炭酸塩又は酸化物の固体表面への銀
のコーテイングが行われるものと思われる。 If the carrier is a substance that does not exhibit basicity, the reduction reaction of silver will not proceed in an acidic solution of hydroxycarboxylic acid as shown in Reference Example 1. Therefore, in the present invention, hydroxycarboxylic acid and silver nitrate produce silver hydroxycarboxylate by the basic action of the solid surface of the alkaline earth metal carbonate or oxide, and this is reduced by the produced aldehyde to form an alkali. It is believed that a coating of silver on the solid surface of an earth metal carbonate or oxide will take place.
本反応で使用されるカルボン酸は炭素数３〜６
個のヒドロキシモノカルボン酸及びヒドロキシジ
カルボン酸類から選ばれた一種もしくは二種以上
の混合物であり、例えば、酒石酸、乳酸、クエン
酸が用いられる。そしてその使用量は硝酸銀１モ
ルに対して0.5モルあればPH値を２に保つことが
出来るが、硝酸銀と等モル量使用するとき銀析出
率が最も高くなる。 The carboxylic acid used in this reaction has 3 to 6 carbon atoms.
One or a mixture of two or more selected from hydroxymonocarboxylic acids and hydroxydicarboxylic acids, such as tartaric acid, lactic acid, and citric acid. If the amount used is 0.5 mol per 1 mol of silver nitrate, the pH value can be maintained at 2, but when it is used in an amount equimolar to that of silver nitrate, the silver precipitation rate becomes the highest.
このように、ヒドロキシカルボン酸は一種の還
元剤として使用されるが、一方水溶液のPHを７以
下に保つて、酸性となるのでこの水溶液において
は通常の固形物、例えば反応器の器壁等に銀が析
出することはない。しかし、アルカリ土類金属炭
酸塩又は酸化物のように界面が塩基性を示すと
き、銀が析出して固体表面を被覆することになる
ものと思われる。 In this way, hydroxycarboxylic acid is used as a kind of reducing agent, but on the other hand, the pH of the aqueous solution must be kept below 7, and since it becomes acidic, it can be mixed with ordinary solids, such as the walls of reactors, etc. Silver does not precipitate. However, when the interface exhibits basicity, such as with alkaline earth metal carbonates or oxides, it is thought that silver will precipitate and coat the solid surface.
銀コーテイングに使用する硝酸銀水溶液の濃度
は0.5〜10重量％がよく、好ましくは１〜３重量
％が適当である。0.5重量％以下の低濃度水溶液
では、銀の析出速度が遅く、また10重量％以上で
は銀析出率が低くなる傾向が見られる。 The concentration of the aqueous silver nitrate solution used for silver coating is preferably 0.5 to 10% by weight, preferably 1 to 3% by weight. When the aqueous solution has a low concentration of 0.5% by weight or less, the silver precipitation rate is slow, and when the concentration is 10% by weight or more, the silver precipitation rate tends to decrease.
銀コーテイングにおける硝酸銀水溶液の温度は
10〜90℃の範囲がよく、好ましくは40〜60℃が好
適である。10℃以下の低温では銀の析出沈着速度
が遅く、長時間を必要とする。また90℃以上では
逆に銀析出率が低下する。 The temperature of silver nitrate aqueous solution in silver coating is
The temperature range is preferably from 10 to 90°C, preferably from 40 to 60°C. At low temperatures below 10°C, the silver precipitation rate is slow and requires a long time. On the other hand, at temperatures above 90°C, the silver precipitation rate decreases.
したがつて硝酸銀水溶液及び還元剤を使用し
て、アルカリ土類、金属炭酸塩又は酸化物の固体
表面に銀を高い析出率で、しかも短時間に析出さ
せるためには、上記条件下で行うことが望まし
い。このように銀コーテイングした固形物は、銀
の殺菌作用を利用した浄水剤の基材として使用さ
れる。 Therefore, in order to deposit silver on the solid surface of alkaline earth metals, metal carbonates, or oxides at a high deposition rate and in a short time using an aqueous silver nitrate solution and a reducing agent, it is necessary to perform the deposition under the above conditions. is desirable. This silver-coated solid material is used as a base material for water purifiers that utilize the bactericidal action of silver.
次に実施例をあげて本発明をさらに具体的に説
明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
１重量％の硝酸銀水溶液10mlと、１重量％の酒
石酸水溶液10mlを混合し平均粒径１mmの大理石10
ｇをこの水溶液中に浸せきする。液温を90℃に保
ちながら一定時間毎にゆるやかにかく拌を行う。
大理石を浸せきしてから約10分経過後、大理石の
表面に銀の析出が始まる。90分間熟成して反応を
終了する。Example 1 10ml of 1% by weight silver nitrate aqueous solution and 10ml of 1% by weight tartaric acid aqueous solution were mixed to produce marble 10 with an average particle size of 1mm.
g is immersed in this aqueous solution. Stir gently at regular intervals while maintaining the liquid temperature at 90°C.
Approximately 10 minutes after the marble is soaked, silver begins to precipitate on the surface of the marble. The reaction was completed by aging for 90 minutes.
大理石表面への銀コーテイング量は、使用した
硝酸銀の銀基準で82％であつた。 The amount of silver coating on the marble surface was 82% based on the silver standard of the silver nitrate used.
実施例 ２
沈降性炭酸カルシウム（試薬一級）に10％のバ
インダー（エチルセルロース系）を使用して直径
1.6mm長さ５mmの押出成型物をつくり、その３ｇ
を１重量％の硝酸銀水溶液５ml及び１重量％の酒
石酸水溶液５mlの混合液中に浸せきした。液温50
℃に保ちながら90分間熟成し銀コーテイングを行
う。反応終了後成型物を液から分離し硝酸イオン
が析出されなくなるまで十分に水洗した。Example 2 Using 10% binder (ethyl cellulose) in precipitated calcium carbonate (first grade reagent), the diameter was
Make an extrusion molded product with a length of 1.6mm and 5mm, and weigh 3g of it.
was immersed in a mixture of 5 ml of a 1% by weight aqueous solution of silver nitrate and 5 ml of an aqueous solution of 1% by weight of tartaric acid. liquid temperature 50
Aged for 90 minutes at ℃ and coated with silver. After the reaction was completed, the molded product was separated from the liquid and thoroughly washed with water until no nitrate ions were precipitated.
炭酸カルシウム成型物への銀コーテイング量は
使用した硝酸銀の銀基準で93％であつた。 The amount of silver coating on the calcium carbonate molded product was 93% based on the silver standard of the silver nitrate used.
実施例 ３
２重量％の硝酸銀水溶液15mlと２重量％の酒石
酸水溶液15mlを混合し、酸化マグネシウム粒（３
mmφ）10ｇを本溶液中に浸せきする。液温を60℃
に保ちながら一定時間毎に、ゆるやかにかく拌を
行う。酸化マグネシウムを浸せきしてから約15分
経過後、酸化マグネシウムの表面に銀の析出が始
まる。90分間熟成して反応を終了する。Example 3 15 ml of a 2% by weight silver nitrate aqueous solution and 15ml of a 2% by weight tartaric acid aqueous solution were mixed, and magnesium oxide particles (3% by weight) were mixed.
mmφ) 10g is immersed in this solution. Liquid temperature 60℃
Stir gently at regular intervals while maintaining the temperature. Approximately 15 minutes after immersing the magnesium oxide, silver begins to precipitate on the surface of the magnesium oxide. The reaction was completed by aging for 90 minutes.
酸化マグネシウム表面への銀コーテイング量
は、使用した硝酸銀の銀基準で44％であつた。 The amount of silver coating on the magnesium oxide surface was 44% based on the silver of the silver nitrate used.
実施例 ４
実施例２で製造した炭酸カルシウムの銀コーテ
イング成型物10ｇを大腸菌群140個／mlを含む河
川水１中に浸せきし20℃の水温を保ち３時間放
置した。その後この試験水を採取し、培養検査し
たところ大腸菌群は13個／mlに減少し、約90％の
大腸菌が殺菌された。Example 4 10 g of the silver-coated calcium carbonate molded product produced in Example 2 was immersed in 1 part of river water containing 140 coliform bacteria/ml and left for 3 hours while maintaining the water temperature at 20°C. This test water was then collected and subjected to culture testing, and the number of coliform bacteria was reduced to 13 per ml, meaning that approximately 90% of the coliform bacteria were sterilized.
実施例 ５
２重量％の硝酸銀水溶液15mlと１重量％の乳酸
水溶液15mlを混合し平均粒径１mmの大理石10ｇを
この水溶液中に浸せきする。液温を60℃に保ちな
がら一定時間毎に、ゆるやかにかく拌を行う。大
理石を浸せきしてから約20分経過後大理石の表面
に銀の析出が始まる。90分間熟成して反応を終了
する。Example 5 15 ml of a 2% by weight silver nitrate aqueous solution and 15 ml of a 1% by weight lactic acid aqueous solution are mixed, and 10 g of marble having an average particle size of 1 mm are immersed in this aqueous solution. Stir gently at regular intervals while maintaining the liquid temperature at 60°C. Approximately 20 minutes after soaking the marble, silver begins to deposit on the surface of the marble. The reaction was completed by aging for 90 minutes.
大理石表面への銀コーテイング量は、使用した
硝酸銀の銀基準で41％であつた。 The amount of silver coating on the marble surface was 41% based on the silver nitrate used.
実施例 ６
２重量％の硝酸銀水溶液15mlと３重量％のクエ
ン酸水溶液15mlを混合し、平均粒径１mmの大理石
10ｇをこの水溶液中に浸せきする。液温を60℃に
保ちながら一定時間毎にゆるやかにかく拌を行
う。大理石を浸せきしてから約30分経過後大理石
の表面に銀の析出が始まる。90分間熟成して反応
を終了する。Example 6 15ml of 2% by weight silver nitrate aqueous solution and 15ml of 3% by weight citric acid aqueous solution were mixed to form marble with an average particle size of 1mm.
Dip 10g into this aqueous solution. Stir gently at regular intervals while maintaining the liquid temperature at 60°C. Approximately 30 minutes after the marble is soaked, silver begins to deposit on the surface of the marble. The reaction was completed by aging for 90 minutes.
大理石表面への銀コーテイング量は使用した硝
酸銀の銀基準で62％であつた。 The amount of silver coating on the marble surface was 62% based on the silver standard of the silver nitrate used.
参考例 １
直径２mmのガラスビーズ３ｇを１重量％の硝酸
銀水溶液５ml及び1.2重量％の酒石酸５mlの混合
液中に浸せきした。液温50℃に保ちながら90分間
熟成した。ガラスビーズを上記混合液から分離
し、十分水洗した後、80℃２時間乾燥し、銀の定
量を行つたが、銀の析出は認められなかつた。Reference Example 1 3 g of glass beads with a diameter of 2 mm were immersed in a mixed solution of 5 ml of a 1% by weight silver nitrate aqueous solution and 5 ml of 1.2% by weight tartaric acid. The mixture was aged for 90 minutes while maintaining the liquid temperature at 50°C. The glass beads were separated from the above mixture, thoroughly washed with water, and then dried at 80° C. for 2 hours. Silver was quantified, but no silver precipitation was observed.
Claims (1)
銀水溶液を混合してPHを１〜５に調整した溶液を
用いてアルカリ土類金属の炭酸塩又は酸化物又は
これらの混合物を処理することを特徴とする、該
固形物表面に銀をコーテイングする方法。 ２ アルカリ土類金属の炭酸塩が炭酸カルシウム
又は炭酸マグネシウムである特許請求の範囲第１
項記載の方法。 ３ アルカリ土類金属の酸化物が酸化マグネシウ
ムである特許請求の範囲第１項記載の方法。 ４ 還元剤が炭素数３〜６個を有するヒドロキシ
モノカルボン酸及びヒドロキシジカルボン酸から
選ばれた一種若しくは二種以上の混合物である特
許請求の範囲第１項、第２項又は第３項記載の方
法。[Scope of Claims] 1 Carbonates or oxides of alkaline earth metals or carbonates or oxides of alkaline earth metals are prepared by mixing an acidic reducing agent and a 0.5 to 10% by weight silver nitrate aqueous solution to adjust the pH to 1 to 5. A method for coating a surface of a solid substance with silver, the method comprising treating a mixture of the above. 2 Claim 1 in which the alkaline earth metal carbonate is calcium carbonate or magnesium carbonate
The method described in section. 3. The method according to claim 1, wherein the alkaline earth metal oxide is magnesium oxide. 4. The reducing agent according to claim 1, 2 or 3, wherein the reducing agent is one or a mixture of two or more selected from hydroxymonocarboxylic acids and hydroxydicarboxylic acids having 3 to 6 carbon atoms. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047385A JPS61190335A (en) | 1985-02-20 | 1985-02-20 | Silver coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047385A JPS61190335A (en) | 1985-02-20 | 1985-02-20 | Silver coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61190335A JPS61190335A (en) | 1986-08-25 |
| JPH0532328B2 true JPH0532328B2 (en) | 1993-05-14 |
Family
ID=12304831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3047385A Granted JPS61190335A (en) | 1985-02-20 | 1985-02-20 | Silver coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61190335A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169682A (en) * | 1990-03-28 | 1992-12-08 | Coral Biotech Co., Ltd. | Method of providing silver on calcium carbonate material such as coral sand |
| JPH0729099B2 (en) * | 1990-03-28 | 1995-04-05 | コーラルバイオテック株式会社 | How to add silver to calcium carbonate |
| JPH0757347B2 (en) * | 1991-04-25 | 1995-06-21 | コーラルバイオテック株式会社 | Method for producing sterilizing purification agent |
| JP6386934B2 (en) * | 2015-02-25 | 2018-09-05 | 太平洋セメント株式会社 | Method for producing metal-supported carbonate particles |
-
1985
- 1985-02-20 JP JP3047385A patent/JPS61190335A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61190335A (en) | 1986-08-25 |
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