JPH0751148B2 - Deodorant material - Google Patents
Deodorant materialInfo
- Publication number
- JPH0751148B2 JPH0751148B2 JP63278709A JP27870988A JPH0751148B2 JP H0751148 B2 JPH0751148 B2 JP H0751148B2 JP 63278709 A JP63278709 A JP 63278709A JP 27870988 A JP27870988 A JP 27870988A JP H0751148 B2 JPH0751148 B2 JP H0751148B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- deodorant material
- salt
- cobalt
- deodorant
- 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
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は硫化水素、アンモニア等の消臭に用いる消臭材
料に関する。TECHNICAL FIELD The present invention relates to a deodorant material used for deodorizing hydrogen sulfide, ammonia and the like.
従来の技術 従来、フタロシアニンに代表されるポルフィリン化合物
は、顔料や染料としての利用のほか、触媒，半導体，光
半導体，ガスセンサ等において多くの応用研究や発明が
開示されている。消臭材料としてのホルフィリン化合物
としては特開昭56−63355号公報にカルボキシル基を有
するポリフィリン化合物が開示されている。具体的なポ
ルフィリン化合物としてはフタロシアニンが用いられ、
鉄またはコバルトフタロシアニンが、H2Sに代表される
酸性ガスに対して触媒的に作用し消臭剤としての性能が
高いことが開示されている。またこのようにフタロシア
ニンにカルボキシル基を導入することにより、NH3に代
表される塩基性ガスの吸着能を付与でき、また繊維など
への担持に際しても、分子分散性がよく、効果的に消臭
繊維を形成できることがわかっている。これは白井汪芳
著「化学」42巻５号、307頁（1987年）、（化学同人）
にも開示されている。2. Description of the Related Art Conventionally, porphyrin compounds typified by phthalocyanines have been used as pigments and dyes, and in addition, many applied researches and inventions have been disclosed in catalysts, semiconductors, optical semiconductors, gas sensors and the like. As a porphyrin compound as a deodorant material, Japanese Patent Laid-Open No. 63-63355 discloses a porphyrin compound having a carboxyl group. Phthalocyanine is used as a specific porphyrin compound,
It is disclosed that iron or cobalt phthalocyanine catalytically acts on an acidic gas represented by H 2 S and has high performance as a deodorant. In addition, by introducing a carboxyl group into phthalocyanine in this way, it is possible to impart the ability to adsorb a basic gas typified by NH 3 and also to have good molecular dispersibility when loaded on fibers, etc. It is known that fibers can be formed. This is written by Kouyoshi Shirai, "Chemistry," Vol. 42, No. 5, 307 (1987), (Chemistry Doujin)
Is also disclosed.
発明が解決しようとする課題 しかしながら、上述の化合物では塩基性ガスに対する吸
着能が低く、また抗菌作用においても不充分な性能しか
得られない面がある。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, the compounds described above have low adsorbing ability for basic gas, and have insufficient antibacterial properties.
そこで本発明は新規な化合物によって、硫化水素やメチ
ルメルカプタン等の酸性臭気に対しても、またアンモニ
ア等の塩基性臭気に対しても大きな効果を有する消臭材
料を提供するものである。Therefore, the present invention provides a deodorant material having a great effect against an acidic odor such as hydrogen sulfide and methyl mercaptan, and a basic odor such as ammonia, by using a novel compound.
課題を解決するための手段 上記課題を解決するため、本発明は新規な消臭材料とし
て、スルフィン化した金属ポルフィリン誘導体と、アン
ミン錯イオン形成能を有する金属イオンとの塩を用いる
ことにより、高性能の消臭作用および、抗菌作用を付与
する。スルフォン化した金属ポリフィリン誘導体には、
酸性ガスに体し酸化触媒能の大きい化合物が適す。具体
的材料としては、鉄，コバルト，ニッケル，マンガン等
のフタロシアニン誘導体がよい。またアンミン錯イオン
形成能の顕著な金属イオンとしては、Ag＋Zn2＋,Mn2＋,
Fe2＋,Cu＋,Cu2＋,Ni2＋,Co2＋等があり、これらは次の
ように１〜６配位のアンミン錯イオン形成能を有してい
る。Means for Solving the Problems In order to solve the above problems, the present invention uses a salt of a sulfinated metal porphyrin derivative and a metal ion having an ammine complex ion-forming ability as a novel deodorant material. Adds deodorant effect and antibacterial effect. Sulfonated metal porphyrin derivatives include
A compound that can withstand an acidic gas and has a large catalytic activity is suitable. As a concrete material, a phthalocyanine derivative such as iron, cobalt, nickel or manganese is preferable. In addition, as the metal ion having a remarkable ability to form an ammine complex ion, Ag + Zn 2 +, Mn 2 +,
Fe 2 +, Cu +, Cu 2 +, Ni 2 +, Co 2 + and the like are present, and they have an ammine complex ion-forming ability of 1 to 6 coordination as follows.
ａ）１配位Ｍ＋（NH3）……Ｍ＋＝Cu＋ ｂ）２配位Ｍ＋（NH3）２……Ｍ＋＝Cu＋,Ag＋ M2＋（NH3）２……M2＋＝Cu2＋ ｃ）３配位Ｍ＋（NH3）３……Ｍ＋＝Cu＋,Ag＋ ｄ）４配位M2＋（NH3）４……M2＋＝Cu2＋ ｅ）６配位M2＋（NH3）６……M2＋＝Zn2＋,Cu2＋,Ni
2＋,Mn2＋,Fe2＋,Co2＋ 本発明における、金属ポリフィリン（M1Po）とアンミン
錯イオン形成能を有する金属イオン（M2 n+）と塩は次の
ような一般式で表わすことができ、アンモニアに対して
次のように反応する。a) One-coordinate M + (NH 3 ) …… M + = Cu + b) Two-coordinate M + (NH 3 ) 2 …… M + = Cu +, Ag + M 2 + (NH 3 ) 2 …… M 2 + = Cu 2 + c) 3-coordinate M + (NH 3 ) 3 ...... M + = Cu +, Ag + d) 4-coordinate M 2 + (NH 3 ) 4 …… M 2 + = Cu 2 + e) 6-coordinate M 2 + (NH 3 ) 6 …… M 2 ＋ ＝ Zn 2 ＋, Cu 2 ＋, Ni
2 +, Mn 2 +, Fe 2 +, Co 2 + In the present invention, the metal porphyrin (M 1 Po), the metal ion (M 2 n + ) capable of forming an ammine complex ion and the salt have the following general formulas. It can be expressed and reacts with ammonia as follows.
（Po:ポルフィリン,A-;アニオン,M1:金属原子） （但し、,m,n,x,yは各々正の数） M1,M2,Aが各々複数の種類の原子よりなる場合もある。(Po: porphyrin, A -; anion, M 1: metal atoms) (However, m, n, x, and y are positive numbers.) M 1 , M 2 , and A may each be composed of a plurality of types of atoms.
金属ポルフィリンをアニオン化した構造としては、側鎖
にスルフォン基，カルボキシル基の導入されたものがあ
る。本発明における具体的化合物としては、コバルトフ
タロンアニンスルフォン酸の銅塩，銀塩，コバルト塩等
が一例として示される。As a structure in which a metalloporphyrin is anionized, there is a structure in which a sulfone group or a carboxyl group is introduced into a side chain. As specific compounds in the present invention, copper salts, silver salts, cobalt salts of cobalt phthalone anine sulfonic acid and the like are shown as an example.
作用 本発明における、スルフォン化した金属ポルフィリン誘
導体とアンミン錯イオン形成能を有する金属イオンとの
塩より成る消臭材料においては、その金属ポルフィリン
構造が触媒的に、硫化水素およびメチルメルカプタン等
の酸性臭気を酸化し、消臭する。一方、塩基性アンモニ
ア臭気に対しては、アンミン錯イオン形成能を有する金
属イオンが錯形成して、アンモニアを吸収する。こうし
てできたアンミン錯イオンは、金属イオンの種類や金属
ポルフィリンアニオン等の影響によって、その安定性が
異なりNH3を条件によって吸収，放出する。水によって
錯イオンが分解する場合もあり、このような化合物にお
いては、この化合物の担持体を水洗いすれば、NH3を放
出し機能を再生させることができる。また、本発明にお
けるポルフィリン誘導体のアニオン基の少くとも１つを
担体との結合に利用し、イオン結合によって担体と結合
させれば、種々の担持物に消臭材料に変えることができ
る。その担体の最も適した一例が繊維であり、ゼオライ
ト等多孔質材である。Action In the present invention, in a deodorant material comprising a salt of a sulfonated metal porphyrin derivative and a metal ion having an ammine complex ion-forming ability, the metal porphyrin structure is catalytically effective to produce an acidic odor such as hydrogen sulfide and methyl mercaptan. Oxidize and deodorize. On the other hand, with respect to the basic ammonia odor, a metal ion having an ammine complex ion forming ability is complexed to absorb ammonia. The thus-produced ammine complex ion has different stability depending on the type of metal ion and the influence of metal porphyrin anion, and absorbs and releases NH 3 depending on the conditions. In some cases, complex ions may be decomposed by water, and in such a compound, washing the support of this compound with water releases NH 3 to regenerate the function. Further, if at least one of the anionic groups of the porphyrin derivative in the present invention is used for binding to the carrier and is bound to the carrier by ionic bonding, it can be converted into various substances to be a deodorant material. One of the most suitable examples of the carrier is fiber, which is a porous material such as zeolite.
実施例 以下、本発明の実施例を説明する。Examples Hereinafter, examples of the present invention will be described.
実施例１ コバルトフタロシアニンテトラルフォン酸ソーダと硫酸
銅の各水溶液を反応させてコバルトフタロシアニンスル
フォン酸銅〔Ａ〕を合成した。この生成物10gをポリウ
レタンワニス（固形分10％）100g中に分散し、ポリエス
テルフィルム上に10μｍの厚さで塗工した。これを用い
てNH3ガスの吸収量を測定したところ、コバルトフタロ
シアニンテトラスルフォン酸の塗工膜（比較例）に比べ
て、３倍の吸収量を示した。Example 1 Cobalt phthalocyanine sulfonate copper [A] was synthesized by reacting each aqueous solution of sodium cobalt phthalocyanine tetralsulfonate and copper sulfate. 10 g of this product was dispersed in 100 g of polyurethane varnish (solid content 10%) and coated on a polyester film to a thickness of 10 μm. When the amount of absorbed NH 3 gas was measured using this, the absorbed amount was three times that of the coating film of cobalt phthalocyanine tetrasulfonic acid (Comparative Example).
実施例２ 硫酸銅の水溶液中にゼオライト粉末を懸濁させた後、コ
バルトフタロシアニンテトラスルフォン酸ソーダを加
え、ゼオライトに担持されたコバルトフタロシアニンス
ルフォンに担持されたコバルトフタロシアニンスルフォ
ン酸銅を得た。得られた粉末を消臭実験に供した。 Example 2 After suspending a zeolite powder in an aqueous solution of copper sulfate, sodium cobalt phthalocyanine tetrasulfonate was added to obtain a cobalt phthalocyanine sulfonate supported on a zeolite-supported cobalt phthalocyanine sulfonate. The obtained powder was subjected to a deodorizing experiment.
実施例３ 第４級アンモニウム基を有するセルロース繊維の塩化物
を、塩化銀の水溶液中に浸漬したのち、これに鉄フタロ
シアニンテトラカルボン酸ソーダを加え、セルロースに
担持された鉄フタロシアニンテトラカルボン酸銀〔Ｂ〕
を得た。これを消臭実験に供した。Example 3 A chloride of cellulose fibers having a quaternary ammonium group was dipped in an aqueous solution of silver chloride, and then sodium iron phthalocyanine tetracarboxylate was added thereto, so that the iron phthalocyanine tetracarboxylate silver supported on cellulose [ B]
Got This was subjected to a deodorant experiment.
実施例４ アクリル繊維を反応性第４級アミン塩化物によって処理
し、４級アンモニウム基を繊維に導入した。この繊維を
塩化第１銅の水溶液中へ浸漬したのち、これにニッケル
フタロシアニンテトラスルフォン酸ソーダを加え、反応
させ、アクリル繊維に担持されたニッケルフタロシアニ
ンテトラスルフォン酸銅を得た。これも同様に消臭実験
に供した。 Example 4 Acrylic fiber was treated with a reactive quaternary amine chloride to introduce quaternary ammonium groups into the fiber. After this fiber was dipped in an aqueous solution of cuprous chloride, nickel phthalocyanine tetrasodium sulfonate was added thereto and reacted to obtain copper nickel phthalocyanine tetrasulfonate supported on acrylic fiber. This was also subjected to the deodorant experiment.
これら実施例１〜４の消臭性能および抗菌性の結果をコ
バルトフタロシアニンテトラスルフォン酸（比較例）と
の相対値で表１に示す。The results of deodorizing performance and antibacterial properties of Examples 1 to 4 are shown in Table 1 as relative values with respect to cobalt phthalocyanine tetrasulfonic acid (comparative example).
発明の効果 以上の実施例の説明より明らかなように、本発明は、ス
ルフォン化した金属ポリフィリン誘導体とアンミン錯イ
オン形成能を有する金属イオンとの塩を用いることによ
り、塩基性臭気にも酸性臭気にも高性能を有する消臭材
料を形成できる。さらに金属キレート結合を多く含むた
め、抗菌性にも優れる高性能な消臭材料である。 EFFECTS OF THE INVENTION As is clear from the description of the above examples, the present invention uses a salt of a sulfonated metal porphyrin derivative and a metal ion having an ammine complex ion-forming ability to produce a basic odor and an acidic odor. Also, a deodorant material having high performance can be formed. Furthermore, since it contains many metal chelate bonds, it is a high-performance deodorant material with excellent antibacterial properties.
Claims (3)
と、アンミン錯イオン形成能を有する金属イオンとの塩
よりなる分子構造を有する結晶粉体よりなり、前記金属
ポルフィリン構造により硫化水素およびメチルメルカプ
タンを触媒的に酸化し、アンモニア分子を前記金属イオ
ンによりアミン錯体として吸収する消臭材料。1. A crystalline powder having a molecular structure comprising a salt of a sulfonated metal porphyrin derivative and a metal ion capable of forming an ammine complex ion, wherein hydrogen sulfide and methyl mercaptan are catalytic by the metal porphyrin structure. A deodorant material that oxidizes into ammonia and absorbs ammonia molecules as amine complexes by the metal ions.
e2+,Co2+,Ni2+より選ばれた少なくとも１種である請求
項（１）記載の消臭材料。2. Metal ions are Cu + , Cu 2+ , Ag + , Zn 2+ , Mn 2+ , F
The deodorant material according to claim 1, which is at least one selected from e 2+ , Co 2+ and Ni 2+ .
塩、銀塩、コバルト塩のうちの少なくとも一種よりなる
請求項（１）記載の消臭材料。3. The deodorant material according to claim 1, comprising at least one of a copper salt, a silver salt and a cobalt salt of cobalt phthalocyanine sulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278709A JPH0751148B2 (en) | 1988-11-04 | 1988-11-04 | Deodorant material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278709A JPH0751148B2 (en) | 1988-11-04 | 1988-11-04 | Deodorant material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02124162A JPH02124162A (en) | 1990-05-11 |
| JPH0751148B2 true JPH0751148B2 (en) | 1995-06-05 |
Family
ID=17601097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63278709A Expired - Lifetime JPH0751148B2 (en) | 1988-11-04 | 1988-11-04 | Deodorant material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0751148B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2630497B2 (en) * | 1990-10-01 | 1997-07-16 | 日鉄鉱業株式会社 | Deodorant composition and deodorant |
| FR2701220B1 (en) * | 1993-02-08 | 1995-04-14 | Inst Francais Du Petrole | Process for catalytic deodorization and reduction of the nitrogen content of slurry tank effluents. |
| JP5885917B2 (en) * | 2010-10-29 | 2016-03-16 | ダイワボウホールディングス株式会社 | Antibacterial deodorant, its fiber structure, and medical / nursing care products |
| KR20140043909A (en) * | 2011-07-14 | 2014-04-11 | 다이와보 홀딩스 가부시키가이샤 | Decontaminating agent for removing harmful substances derived from flying dust and microorganisms, cellulose fiber, and fiber structure |
| JP2017088697A (en) * | 2015-11-06 | 2017-05-25 | 真庭バイオケミカル株式会社 | Modified cellulose fiber |
| CN114702846B (en) * | 2022-04-24 | 2023-03-28 | 杭州意能电力技术有限公司 | Water-based antibacterial coating and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS627000A (en) * | 1985-02-06 | 1987-01-13 | 大和紡績株式会社 | Deodorizing wet nonwoven fabric |
| JPH0741133B2 (en) * | 1986-07-16 | 1995-05-10 | エヌオーケー株式会社 | Deodorant porous membrane |
| JPH01320061A (en) * | 1988-06-21 | 1989-12-26 | Nippon Carbide Ind Co Inc | Compound for deodorizing |
-
1988
- 1988-11-04 JP JP63278709A patent/JPH0751148B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02124162A (en) | 1990-05-11 |
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