JPH0235688B2 - NISANKAENSOGASUNOKANMANNAHATSUSEIHOHO - Google Patents
NISANKAENSOGASUNOKANMANNAHATSUSEIHOHOInfo
- Publication number
- JPH0235688B2 JPH0235688B2 JP17173984A JP17173984A JPH0235688B2 JP H0235688 B2 JPH0235688 B2 JP H0235688B2 JP 17173984 A JP17173984 A JP 17173984A JP 17173984 A JP17173984 A JP 17173984A JP H0235688 B2 JPH0235688 B2 JP H0235688B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorine dioxide
- composition
- chlorite
- dioxide gas
- aqueous solution
- 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
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 114
- 239000004155 Chlorine dioxide Substances 0.000 claims description 57
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910001919 chlorite Inorganic materials 0.000 claims description 9
- 229910052619 chlorite group Inorganic materials 0.000 claims description 9
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 238000005259 measurement Methods 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 4
- 229960002218 sodium chlorite Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 2
- KEBDNKNVCHQIJU-UHFFFAOYSA-N 2-Methylpropyl 3-methylbutanoate Chemical compound CC(C)COC(=O)CC(C)C KEBDNKNVCHQIJU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
Description
（発明の技術分野）
本発明は二酸化塩素ガスの緩慢な発生方法に関
するものである。
（従来の技術及び問題点）
二酸化塩素は強い酸化力を持つているので、脱
臭剤、防腐剤、防カビ剤、殺藻剤、殺菌剤、消毒
剤、漂白剤等として使われている。
これらの用途に向けて、安定化二酸化塩素水溶
液や二酸化塩素ガスを発生する粉末状若しくは粒
状の組成物が業務用又は一般家庭用として市販さ
れており、これらの固体状組成物については種々
の研究が行われている。
例えば、亜塩素酸ナトリウムや安定化二酸化塩
素の水溶液等の二酸化塩素含有水溶液を塩基性吸
着剤に吸着させた組成物（特公昭48−32079）、亜
塩素酸塩又は安定化二酸化塩素をPH８以上のアル
カリ性固体物質及びアルカリ性酸化剤と混合した
組成物（特開昭58−161904）、或いは、花弁状結
晶構造をもつ珪酸カルシウムに安定化二酸化塩素
水溶液を吸着させ、鉄分を二酸化塩素揮散速度調
整用として添加した組成物（特開昭57−168977）
等があるが、いずれも安定性が不十分であつて商
品流通時や貯蔵中に二酸化塩素を放出し続けた
り、使用時の有効期間を縮めたりする虞れがあ
る。
また、二酸化塩素含有アルカリ水溶液をPH8.5
〜9.0の塩基性吸着剤に吸着させた粉末固体組成
物に、使用の際PH６以下の固体酸性粉末を添加混
合して二酸化塩素を発生させる（特公昭48−
32079）方法も知られているが、このものは貯蔵
中は長期間安定性はあるとしても、使用の際混合
操作を行わねばならぬ点が使用者に不便である上
に、ほゞ安定した二酸化塩素発生速度を長期間に
亙つて維持することは難しい。
（発明の目的）
発明者らは貯蔵期間中長期に亙つて安定であ
り、使用に際しては簡便且つ安全な二酸化塩素発
生持続性の優れた方法を得る目的で鋭意検討を行
つた。その結果、塩基性固体物質に保持された二
酸化塩素含有組成物に適当な蒸気圧を有する酸等
の蒸気を作用させれば上記目的を十分に達成し得
ることを見出し本発明を完成するに至つたもので
ある。
（発明の構成）
本発明は、亜塩素酸塩の粉体又は亜塩素酸塩若
しくは安定化二酸化塩素の水溶液（以下二酸化塩
素発生剤という。）を塩基性固体物質に混合又は
吸着させた組成物（以下二酸化塩素含有組成物と
いう。）に、酸若しくはエステルの蒸気を接触せ
しめることを特徴とする、二酸化塩素ガスの緩慢
な発生方法である。
本発明に用いられる二酸化塩素発生剤としての
亜塩素酸塩は亜塩素酸のアルカリ金属塩又はアル
カリ土類金属塩のいずれでも用いられるが、経済
的で実用的な物質は亜塩素酸トナリウムである。
本発明の亜塩素酸塩はこれを含む粉体又は水溶
液が使用できる。
本発明に用いられるもう１つの二酸化塩素発生
剤である安定化二酸化塩素水溶液は公知のもので
ある。即ち過炭酸ナトリウム又は過ホウ酸ナトリ
ウム等の安定剤を含有する二酸化塩素水溶液を使
用することができる。
本発明に用いられる塩基性固体物質としては粉
末状又は粒状の燐酸三ナトリウム、珪酸カルシウ
ム、珪酸マグネシウム、アルミノ珪酸塩、シリカ
ゲル、パーライト、アルミナ等の天然品又は合成
のいずれも使用することができる。但し、二酸化
塩素発生剤から二酸化塩素の発生を促進するよう
な鉄その他重金属等の不純物の含有量の少ないも
のが望ましい。
また、中性固体物質でも水酸化ナトリウム、炭
酸ナトリウム等塩基性物質を添加してアルカリ性
領域に変えることにより用いることができる。
本発明の二酸化塩素含有組成物は上記塩基性固
体物質に二酸化塩素発生剤を保持させて製造され
る。該発生剤が液状の場合は吸着性の該固体物質
に吸着させ、粉末状の場合は該固体物質に混合付
着させる。
該組成物が長期間安定で且つ使用時に容易に二
酸化塩素ガスを発生し得るためにはPH８〜12、好
ましくはPH8.5〜11.0の範囲でなければならない。
PH８未満では使用初期に急激な二酸化塩素ガス発
生の恐れがある上、長期保存性に劣る。アルカリ
性のPHが高い場合、保存性に優れるもののPH12を
越える場合は使用初期の二酸化塩素ガス発生まで
の待ち時間が長くなる等不具合の生じる恐れがあ
る。
該組成物の粒度は対象物質や使用目的、使用形
態に応じて適切な範囲を選択すればよく、特に限
定されない。
本発明に用いられる、二酸化塩素ガスの発生を
促進する酸及び／又はエステル類（以下揮散助剤
という。）は使用時の温度条件で対象・用途に応
じた適当な蒸気圧を有するものであればよく特に
限定されないが、例えば、酢酸、プロピオン酸、
酪酸、アクリル酸、無水コハク酸等のカルボン酸
類、乳酸エチル、しゆう酸ジメチル、イソ吉草酸
イソブチル、イソ酪酸イソブチル等のエステル類
の群の１種又は２種以上を有効に用いることがで
きる。
これら揮散助剤は、低濃度の二酸化塩素ガスを
必要とする場合は取扱いに便利な固体を使うこと
もできるが、該助剤の大部分が常温で液状である
ため、脱脂綿、ガーゼ、スポンジ、紙、シリカゲ
ル、アルミナ等の固体に担持させれば、貯蔵や使
用に便利且つ安全である。
本発明の方法を実施するに当つては、二酸化塩
素含有組成物に揮散助剤の蒸気を接触させること
によつて、該組成物の表面で二酸化塩素発生剤が
酸性化され、二酸化塩素ガスの発生が促される。
揮散助剤がエステル類の場合は空気中の水分によ
つて分解生成した酸が上記発生剤の酸性化を起し
二酸化塩素ガスの発生に至る。
二酸化塩素ガスの揮散速度又は濃度は、該組成
物及び揮散助剤の種類や接触方法を適切に選択す
ることによつて調整乃至制御することができ、ま
た両者を隔離することによつて極めて容易に二酸
化塩素ガスの発生を中断乃至停止させることがで
きる。
本発明の二酸化塩素含有組成物に揮散助剤の蒸
気を接触させる手法としては、極く普通の構造の
ものから適宜選択すればよい。例えば、仕切板で
区画した容器の両室に夫々該組成物と揮散助剤を
充填しておき、使用に際し仕切板を取り除いて両
者を接触させる。適時仕切板をはめこむことによ
り接触中断、従つて二酸化塩素発生を中断するこ
とができる。
立型カラム充填方式も上記と同様に使用するこ
とができる。
（実施例）
実施例 １
粉末状燐酸三ナトリウム（５重量％水溶液のPH
12.3）100重量部と25重量％亜塩素酸ナトリウム
水溶液（PH12.1）30重量部を均一に混合し、二酸
化塩素含有組成物を得た。このものは粉末状であ
つた。
内径３cm×高さ30cmの円筒状ガラス容器の底部
に10ｇの酸を滲みこませた脱脂綿を置く。その上
部に塩化ビニール性多孔板及び脱脂綿を敷き、そ
の上に上記組成物の粉末15ｇを一様に撒いた。
上部開放の状態で気温28℃で二酸化塩素ガスを
発生させ、ガラス容器の上部空間よりそのガスを
吸引して、ガス検知管にて二酸化塩素ガス濃度を
測定した。測定結果を表１に示した。
TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for slowly generating chlorine dioxide gas. (Prior Art and Problems) Since chlorine dioxide has strong oxidizing power, it is used as a deodorizer, preservative, fungicide, algaecide, disinfectant, disinfectant, bleach, etc. For these uses, stabilized chlorine dioxide aqueous solutions and powdered or granular compositions that generate chlorine dioxide gas are commercially available for commercial or household use, and various studies have been conducted on these solid compositions. is being carried out. For example, compositions in which an aqueous solution containing chlorine dioxide, such as an aqueous solution of sodium chlorite or stabilized chlorine dioxide, is adsorbed on a basic adsorbent (Japanese Patent Publication No. 48-32079), chlorite or stabilized chlorine dioxide with a pH of 8 or higher. A composition mixed with an alkaline solid substance and an alkaline oxidizing agent (Japanese Unexamined Patent Publication No. 58-161904), or a stabilized chlorine dioxide aqueous solution is adsorbed on calcium silicate having a petal-like crystal structure, and the iron content is used to adjust the volatilization rate of chlorine dioxide. (Japanese Patent Application Laid-Open No. 168977)
However, all of them have insufficient stability and may continue to release chlorine dioxide during product distribution or storage, or may shorten the shelf life when used. In addition, an alkaline aqueous solution containing chlorine dioxide has a pH of 8.5.
During use, a solid acidic powder with a pH of 6 or less is added to a powder solid composition adsorbed on a basic adsorbent with a pH of ~9.0 to generate chlorine dioxide.
32079) method is also known, but although this method may be stable for a long period of time during storage, it is inconvenient for the user to have to perform a mixing operation before use, and it is not nearly stable. It is difficult to maintain the chlorine dioxide generation rate over a long period of time. (Purpose of the Invention) The inventors have conducted intensive studies with the aim of obtaining a method that is stable over a long period of time during storage, is simple and safe to use, and has excellent sustainability in generating chlorine dioxide. As a result, they discovered that the above object could be fully achieved by applying vapor of an acid or the like having an appropriate vapor pressure to a chlorine dioxide-containing composition held in a basic solid substance, and completed the present invention. It is ivy. (Structure of the Invention) The present invention provides a composition in which a powder of chlorite or an aqueous solution of chlorite or stabilized chlorine dioxide (hereinafter referred to as a chlorine dioxide generator) is mixed or adsorbed onto a basic solid substance. This is a method for slowly generating chlorine dioxide gas, which is characterized by bringing acid or ester vapor into contact with a chlorine dioxide-containing composition (hereinafter referred to as a chlorine dioxide-containing composition). Chlorite as a chlorine dioxide generating agent used in the present invention can be either an alkali metal salt or an alkaline earth metal salt of chlorite, but an economical and practical substance is tonium chlorite. . The chlorite of the present invention can be used as a powder or an aqueous solution. The stabilized chlorine dioxide aqueous solution, which is another chlorine dioxide generator used in the present invention, is a known one. That is, an aqueous solution of chlorine dioxide containing a stabilizer such as sodium percarbonate or sodium perborate can be used. As the basic solid substance used in the present invention, natural or synthetic materials such as powdered or granular trisodium phosphate, calcium silicate, magnesium silicate, aluminosilicate, silica gel, pearlite, alumina, etc. can be used. However, it is desirable that the chlorine dioxide generating agent contains a small amount of impurities such as iron and other heavy metals that promote the generation of chlorine dioxide. Further, even neutral solid substances can be used by adding basic substances such as sodium hydroxide or sodium carbonate to change the substance to an alkaline region. The chlorine dioxide-containing composition of the present invention is produced by holding a chlorine dioxide generator in the basic solid material. When the generator is in liquid form, it is adsorbed onto the adsorbent solid substance, and when it is in powder form, it is mixed and adhered to the solid substance. In order for the composition to be stable for a long period of time and to be able to easily generate chlorine dioxide gas during use, the pH must be in the range of 8 to 12, preferably 8.5 to 11.0.
If the pH is less than 8, there is a risk of rapid generation of chlorine dioxide gas at the beginning of use, and long-term storage stability is poor. If the pH of the alkaline product is high, it has excellent storage stability, but if the pH exceeds 12, problems may occur, such as a longer waiting time until chlorine dioxide gas is generated at the beginning of use. The particle size of the composition is not particularly limited and may be selected within an appropriate range depending on the target substance, purpose of use, and form of use. The acids and/or esters (hereinafter referred to as volatilization aids) used in the present invention that promote the generation of chlorine dioxide gas may have an appropriate vapor pressure depending on the target and application under the temperature conditions at the time of use. For example, acetic acid, propionic acid,
One or more of the group consisting of carboxylic acids such as butyric acid, acrylic acid, and succinic anhydride, and esters such as ethyl lactate, dimethyl oxalate, isobutyl isovalerate, and isobutyl isobutyrate can be effectively used. When low-concentration chlorine dioxide gas is required, solid forms can be used as these volatilization aids, which are convenient to handle, but most of these aids are liquid at room temperature, so absorbent cotton, gauze, sponge, If it is supported on solids such as paper, silica gel, alumina, etc., it is convenient and safe for storage and use. In carrying out the method of the present invention, the chlorine dioxide generating agent is acidified on the surface of the composition by contacting the chlorine dioxide-containing composition with the vapor of the volatilization aid, and the chlorine dioxide gas is Occurrence is encouraged.
When the volatilization aid is an ester, the acid decomposed by moisture in the air acidifies the generator, leading to the generation of chlorine dioxide gas. The volatilization rate or concentration of chlorine dioxide gas can be adjusted or controlled by appropriately selecting the type and contact method of the composition and volatilization aid, and can be extremely easily controlled by isolating the two. It is possible to interrupt or stop the generation of chlorine dioxide gas. The method for bringing the vapor of the volatilization aid into contact with the chlorine dioxide-containing composition of the present invention may be appropriately selected from those having extremely common structures. For example, both chambers of a container separated by a partition plate are filled with the composition and the volatilization aid, respectively, and before use, the partition plate is removed and the two are brought into contact. By fitting the partition plate in a timely manner, the contact and therefore the generation of chlorine dioxide can be interrupted. Vertical column packing systems can also be used in the same manner as above. (Example) Example 1 Powdered trisodium phosphate (PH of 5% aqueous solution)
12.3) 100 parts by weight and 30 parts by weight of a 25% by weight aqueous sodium chlorite solution (PH12.1) were uniformly mixed to obtain a chlorine dioxide-containing composition. This material was in powder form. Place absorbent cotton soaked with 10 g of acid at the bottom of a cylindrical glass container with an inner diameter of 3 cm and a height of 30 cm. A perforated vinyl chloride plate and absorbent cotton were placed on top of it, and 15 g of the powder of the above composition was evenly spread thereon. Chlorine dioxide gas was generated at a temperature of 28°C with the top open, and the gas was sucked from the upper space of the glass container, and the chlorine dioxide gas concentration was measured using a gas detection tube. The measurement results are shown in Table 1.
【表】
実施例 ２
粉末状の合成ゼオライト（５重量％スラリーの
PH11.2）100重量部に25重量％亜塩素酸ナトリウ
ム水溶液（PH12.1）35重量部を均一に混合し、二
酸化塩素含有組成物を得た。このものは粉末状で
あつた。
実施例１と同様の装置・方法で二酸化塩素ガス
を発生させ、実施例１と同様にサンプリング、測
定した結果を表２に示した。[Table] Example 2 Powdered synthetic zeolite (5% by weight slurry)
35 parts by weight of a 25% by weight aqueous sodium chlorite solution (PH12.1) was uniformly mixed with 100 parts by weight of PH11.2) to obtain a chlorine dioxide-containing composition. This material was in powder form. Chlorine dioxide gas was generated using the same equipment and method as in Example 1, and the results of sampling and measurement in the same manner as in Example 1 are shown in Table 2.
【表】
実施例 ３
酸の代りにエステル類を用いた外は実施例２と
全く同様にして行つた測定結果を表３に示した。[Table] Example 3 Table 3 shows the results of measurements carried out in exactly the same manner as in Example 2, except that esters were used instead of acids.
【表】
比較例 １
実施例２で調整したのと同様の二酸化塩素含有
組成物15ｇを乳酸エチル４ｇと均一に混合し、実
施例２と同様の円筒状ガラス容器の底部に入れて
二酸化塩素ガスを発生させた外は実施例２と同様
にして行つた測定結果を表４に示した。[Table] Comparative Example 1 15 g of a chlorine dioxide-containing composition similar to that prepared in Example 2 was uniformly mixed with 4 g of ethyl lactate, and the mixture was placed in the bottom of a cylindrical glass container similar to that of Example 2, and chlorine dioxide gas was added. Table 4 shows the results of measurements conducted in the same manner as in Example 2, except that .
【表】
実施例 ４
粉末状合成珪酸カルシウム（５重量％スラリー
のPH10.4）100重量部に粉末状亜塩素酸ナトリウ
ム（含有率約80重量％）10重量部を均一に混合
し、二酸化塩素含有組成物を得た。
該組成物及びｎ−酪酸を用いた以外は、実施例
１と同様にして行つた測定結果を表５に示した。[Table] Example 4 100 parts by weight of powdered synthetic calcium silicate (PH 10.4 of 5% slurry) was uniformly mixed with 10 parts by weight of powdered sodium chlorite (content about 80% by weight), and chlorine dioxide was added. A containing composition was obtained. Table 5 shows the results of measurements conducted in the same manner as in Example 1, except that the composition and n-butyric acid were used.
【表】
実施例 ５
粉末状燐酸三ナトリウム（５重量％水溶液のPH
12.3）100重量部に５重量％の安定化二酸化塩素
水溶液50重量部を、急激な発熱を避けるため、少
量ずつゆつくり滴下混合し、二酸化塩素含有組成
物を得た。
該組成物を用いた以外は実施例１と同様にして
行つた測定結果を表６に示した。[Table] Example 5 Powdered trisodium phosphate (PH of 5% aqueous solution)
12.3) To 100 parts by weight, 50 parts by weight of a 5% by weight stabilized chlorine dioxide aqueous solution was slowly added dropwise to 100 parts by weight in order to avoid rapid heat generation, thereby obtaining a chlorine dioxide-containing composition. Table 6 shows the results of measurements conducted in the same manner as in Example 1 except that the composition was used.
【表】
（発明の効果）
本発明を用いて、二酸化塩素含有組成物に揮散
助剤の蒸気を接触させることにより、各実施例で
明らかなように、両薬剤の種類や接触させ方に応
じて、長期間に亙つて使用者を望む二酸化塩素ガ
ス濃度範囲を維持することができる。また、特に
揮散蒸気が満遍なく該組成物と接触するので、使
用初期に高濃度の二酸化塩素ガスが発生する危険
は全くない。
更に何時でも、二酸化塩素ガスの発生中断域い
は再開を繰り返すことが極めて容易にでき、ガス
濃度調整も容易である。
本発明の二酸化塩素含有組成物は貯蔵期間中極
めて安全な、安定した状態を維持することができ
る。
更に、揮散助剤がガーゼ等の布状体やシリカゲ
ル等に担持させることにより、該組成物及び助剤
の両者とも固体であるためどんな場所でも使用す
ることができる。
このように、本発明は材料の保存性、使用の簡
便性、優れた効能持続性等信頼性の高い優れた方
法ということができる。[Table] (Effects of the Invention) Using the present invention, by bringing the vapor of the volatilization aid into contact with the chlorine dioxide-containing composition, it is possible to Therefore, the user can maintain the desired chlorine dioxide gas concentration range for a long period of time. In addition, especially since the vaporized vapor comes into contact with the composition evenly, there is no risk of generating high-concentration chlorine dioxide gas at the initial stage of use. Furthermore, it is extremely easy to repeatedly stop and restart the generation of chlorine dioxide gas at any time, and the gas concentration can be easily adjusted. The chlorine dioxide-containing compositions of the present invention can remain extremely safe and stable during storage. Furthermore, by supporting the volatilization aid on a cloth-like material such as gauze, silica gel, etc., the composition and the aid are both solid, so that they can be used anywhere. As described above, the present invention can be said to be an excellent method with high reliability in terms of material storage stability, ease of use, and excellent long-lasting efficacy.
Claims (1)
安定化二酸化塩素の水溶液を塩基性固体物質に混
合又は吸着させた組成物に、酸若しくはエステル
の蒸気を接触せしめることを特徴とする二酸化塩
素ガスの緩慢な発生方法。1 Dioxidation characterized by bringing acid or ester vapor into contact with a composition in which chlorite powder or an aqueous solution of chlorite or stabilized chlorine dioxide is mixed or adsorbed on a basic solid substance. A slow method of generating chlorine gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17173984A JPH0235688B2 (en) | 1984-08-17 | 1984-08-17 | NISANKAENSOGASUNOKANMANNAHATSUSEIHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17173984A JPH0235688B2 (en) | 1984-08-17 | 1984-08-17 | NISANKAENSOGASUNOKANMANNAHATSUSEIHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6148404A JPS6148404A (en) | 1986-03-10 |
| JPH0235688B2 true JPH0235688B2 (en) | 1990-08-13 |
Family
ID=15928784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17173984A Expired - Lifetime JPH0235688B2 (en) | 1984-08-17 | 1984-08-17 | NISANKAENSOGASUNOKANMANNAHATSUSEIHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0235688B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6605304B1 (en) * | 1998-02-09 | 2003-08-12 | Bernard Technologies, Inc. | Silicate-containing powders providing controlled, sustained gas release |
| GB0609485D0 (en) * | 2006-05-12 | 2006-06-21 | Glaxo Group Ltd | Chlorine dioxide tooth whitening composition |
| JP5664838B2 (en) * | 2008-04-02 | 2015-02-04 | 有限会社クリーンケア | A method for producing chlorine dioxide safely and efficiently at any concentration at any time |
| EP2554513B1 (en) * | 2010-03-26 | 2018-10-03 | Taiko Pharmaceutical Co., Ltd. | Device for generating chlorine dioxide |
| CN103906704B (en) | 2012-10-24 | 2016-05-11 | 株式会社阿玛特拉 | Chlorine dioxide produces agent packaging and manufacture method and store method |
-
1984
- 1984-08-17 JP JP17173984A patent/JPH0235688B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6148404A (en) | 1986-03-10 |
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