JP3830993B2 - Deodorant antibacterial material carrying water-soluble metal phthalocyanine derivative - Google Patents

Description

【０００８】
本発明の金属フタロシアニン誘導体は、文献公知（例えば、Chem. Lett.,1991,1877、Photochem.Photobiol.,1990,51,351、J.Heterocycle.Chem.,1981,18,1613、等）の化３（式中、ｎは２〜６の整数を表す。）で表される化合物を出発物質として化４（式中、ｎは２〜６の整数、Ｍはコバルト原子を表す。）で表される化合物に変換後、これをアルキル化することにより製造される。
【０００９】
【化３】

【００１０】
【化４】

【００１１】
化３で表される化合物から化４で表される化合物への変換は、塩化コバルト存在下、アンモニア飽和ジメチルアミノエタノール中で実施される。反応温度は１５０〜２００℃、反応時間は１０〜７２時間程度である。上記化４で表される化合物は、例えばアルミナカラムクロマトグラフィー等により単離・精製することができる。
【００１２】
化４で表される化合物のアルキル化は、化５（式中、ｍは０〜５の整数、Ｘは臭素原子を表す。）で表されるアルキルハライドと反応することにより実施される。
【００１３】
【化５】

【００１４】
用いられるアルキルハライドとしては、具体的には、臭化メチル、臭化エチル、臭化プロピル、臭化ブチル、臭化ペンチル、臭化ヘキシルを例示することができる。反応は溶媒の存在下実施されるが、使用される溶媒としては反応を阻害しないものであれば適当であるが、ジメチルホルムアミドが特に好ましい。反応温度は室温から１００℃、反応時間は５〜４８時間程度である。反応終了後、目的物は常法により、例えば、ジメチルホルムアミド及びジメチルスルフォキシドを溶離溶媒とし、シリカゲルカラムクロマトグラフィー法により、容易に単離される。
【００１５】
本発明では、更に化２で表される化合物を含有した消臭抗菌材が提供される。本発明の化２で表される化合物は、そのままの状態で水に容易に溶解するため、１％程度の水溶液に、消臭抗菌機能付与物、例えば不織布、紙、パルプ等を浸し、加熱定着するだけで、容易に消臭抗菌材とすることができる。
【００１６】
【実施例】
以下、参考例と実施例を挙げて、本発明を詳細に説明する。
参考例１ ４−（２’−ジメチルアミノエトキシ）フタロニトリル０．８ｇ、無水塩化コバルト０．２４ｇを２−ジメチルアミノエタノール５０ｍｌに溶解し、１３０℃で４８時間アンモニアガスをバブリングさせながら反応した。反応終了後、水２００ｍｌを加え、活性アルミナカラムに吸着後、ジメチルホルムアミドで溶離することにより、テトラキス（２−ジメチルアミノエトキシ）フタロシアニンコバルト(II)、ＣｏＰｃ（Ｏ（ＣＨ₂）₂Ｎ（ＣＨ₃）₂）₄、を得た（収率４０％）。
^１Ｈ−ＮＭＲ（ＤＭＳ０−ｄ６）
δ3.40(s,24H),4.13-5.12(s,16H),7.91-9.40(m,12H)ＵＶ／ＶＩＳ（ＤＭＦ）
λmax＝６７８，６１２，３４８ｎｍＩＲ（ＫＢｒ）
１２３１ｃｍ^-1（Ａｒ−Ｏ−ＣＨ₂）
元素分析値（Ｃ₁₂Ｈ₁₅Ｎ₃Ｏとして）
計算値 Ｃ：６２．１３％ Ｈ：６．４７％ Ｎ：１８．１２％ 測定値 Ｃ：６２．５５％ Ｈ：５．８８％ Ｎ：１７．７６％
【００１７】
得られたテトラキス（２−ジメチルアミノエトキシ）フタロシアニンコバルト(II)を、４０倍モルの沃化メチルとともにジメチルホルムアミド５ｍｌに溶解し、室温で２４時間反応した。反応終了後、溶媒を濃縮し、残渣をカラムクロマトグラフィー（シリカゲル）で処理することにより、化合物１、テトラキス（２−トリメチルアミノエトキシ）フタロシアニンコバルト(II)ヨウ素塩（ｍ＝０、ｎ＝２）を得た（収率６８％）。なお、化合物１は、水１Ｌに１０ｇ程度溶解する。
^１Ｈ−ＮＭＲ（ＤＭＳ０−ｄ６）
δ3.40(s,36H),4.15-5.18(s,16H),7.98-9.82(m,12H)ＵＶ／ＶＩＳ（ＤＭＦ）
λmax＝６７８，６１２，３４８ｎｍ
元素分析値（Ｃ₅₂Ｈ₆₄Ｎ₁₂Ｏ₄ＣｏＩ₄として）
計算値 Ｃ：３９．９２％ Ｈ：４．６４％ Ｎ：１０．７５％ 測定値 Ｃ：４１．２１％ Ｈ：４．２５％ Ｎ：１０．９６％
【００１８】
実施例１ ４−（２’−ジメチルアミノエトキシ）フタロニトリル０．８ｇ、無水塩化コバルト０．２４ｇを２−ジメチルアミノエタノール５０ｍｌに溶解し、１３０℃で４８時間アンモニアガスをバブリングさせながら反応した。反応終了後、水２００ｍｌを加え、活性アルミナカラムに吸着後、ジメチルホルムアミドで溶離することにより、テトラキス（２−ジメチルアミノエトキシ）フタロシアニンコバルト(II)、ＣｏＰｃ（Ｏ（ＣＨ₂）₂Ｎ（ＣＨ₃）₂）₄、を得た。
得られたテトラキス（２−ジメチルアミノエトキシ）フタロシアニンコバルト(II)を、４０倍モルの臭化エチルとともにジメチルホルムアミド５ｍｌに溶解し、室温で２４時間反応した。反応終了後、溶媒を濃縮し、残渣をカラムクロマトグラフィー（シリカゲル）で処理することにより、化合物２（ｍ＝１、ｎ＝２）を得た（収率３５％）。
^１Ｈ−ＮＭＲ（ＤＭＳ０−ｄ６）
δ1.38(s,12H),3.51(s,32H),4.17-5.22(s,16H),7.96-9.28(m,12H)
【００１９】
実施例２〜４ 実施例１において、臭化エチルに代えて臭化プロピル、臭化ブチル及び臭化ペンチルを用い、６０℃にて反応させた以外は実施例１と同一に実施することにより化合物３〜５（ｍ＝２〜４、ｎ＝２）を得た。
参考例２ 実施例１において、臭化エチルに代えて臭化ヘキシルを用い、６０℃にて反応させた以外は実施例１と同一に実施することにより化合物６（ｍ＝５、ｎ＝２）を得た。
得られた化合物３〜６の収率、及び^１Ｈ−ＮＭＲの結果を表１に示す。なお、表１中、化６は下記の式（式中、Ｍはコバルト原子を表す。）である。
【００２０】
【化６】

【００２１】
【表１】

【００２２】
実施例５ ４−（６’−ジメチルアミノヘキシロキシ）フタロニトリル１．０ｇ、無水塩化コバルト０．２４ｇを２−ジメチルアミノエタノール５０ｍｌに溶解し、１３０℃で４８時間アンモニアガスをバブリングさせながら反応した。反応終了後、水２００ｍｌを加え、活性アルミナカラムに吸着後、ジメチルホルムアミドで溶離することにより、テトラキス（６−ジメチルアミノヘキシロキシ）フタロシアニンコバルト(II)、ＣｏＰｃ（Ｏ（ＣＨ₂）₆Ｎ（ＣＨ₃）₂）₄、を得た（収率４２％）。
^１Ｈ−ＮＭＲ（ＤＭＳ０−ｄ６）
δ3.40(s,24H),4.13-5.12(s,64H),7.91-9.40(m,12H)ＵＶ／ＶＩＳ（ＤＭＦ）
λmax＝６７８，６１２，３４８ｎｍＩＲ（ＫＢｒ）
１２３１ｃｍ^-1（Ａｒ−Ｏ−ＣＨ₂）
元素分析値（Ｃ₆₄Ｈ₈₄Ｎ₁₂Ｏ₄Ｃｏとして）
計算値 Ｃ：６６．７２％ Ｈ：７．９９％ Ｎ：１４．５９％ 測定値 Ｃ：６７．２１％ Ｈ：８．１０％ Ｎ：１４．４５％
【００２３】
得られたテトラキス（６−ジメチルアミノヘキシロキシ）フタロシアニンコバルト(II)を、４０倍モルの臭化メチルとともにジメチルホルムアミド５ｍｌに溶解し、室温で２４時間反応した。反応終了後、溶媒を濃縮し、残渣をカラムクロマトグラフィー（シリカゲル）で処理することにより、化合物７、テトラキス（６−トリメチルアミノヘキシロキシ）フタロシアニンコバルト(II)臭素塩（ｍ＝０、ｎ＝６）を得た（収率４２％）。
元素分析値（Ｃ₆₈Ｈ₉₆Ｎ₁₂Ｏ₄ＣｏＢｒ₄として）
計算値 Ｃ：５３．７１％ Ｈ：６．３１％ Ｎ：１１．０６％ 測定値 Ｃ：５２．１５％ Ｈ：６．８１％ Ｎ：１０．１９％
【００２４】
実施例６〜１３ 参考例および実施例で得た化合物１〜７の１％の水溶液２０部に、アクリル／綿＝１／１の不織布、あるいはパルプ１部を漬け、９０℃に加熱定着処理後、水洗・脱液・乾燥することにより、消臭・抗菌素材を得た。得られた消臭・抗菌素材について、消臭・抗菌効果を評価し、結果を表２に記載した。なお、評価方法は以下の通りである。
【００２５】
１．消臭効果測定方法 実施例６〜１３で得た素材１ｇを３Ｌのデシケーターに入れ、硫化水素５ＰＰＭを含む悪臭空気と置換し、２４時間後に臭気残存を官能試験法にて確認した。
２．抗菌効果測定方法
（１）供与菌…Bacillus subtilisを培養液（ペプトン５ｇ、肉エキス３ｇ、クエン酸ナトリウム１０ｇ、寒天２０ｇを水１０００ｍｌに溶かしてｐＨ６．５〜６．６に調整したもの）で３５℃で１週間培養し、胞子調製後培養液を６５℃で３０分間加熱し供試菌液とした。
（２）培地…滅菌した寒天培地（ペプトン１０ｇ、肉エキス５ｇ、寒天１５ｇを水１０００ｍｌに溶かして調製したもの）２０ｍｌと供試菌液０．１ｍｌを混合したものを、内径約９０ｍｍのペトリ皿に流し込み室温にて放置して固化させた。
（３）試料…実施例６〜１３で得た素材を、径約９ｍｍの円形に切りとり滅菌処理して試料とした。
（４）試験方法…円形の試料をピンセットで培地の表面に置き、３５℃にて１８時間放置後、透明ゾーンを観察した。ハロー部分の大きさより抗菌力を判断した。
【００２６】
【表２】

【００２７】
【発明の効果】
以上説明してきたように、本発明によれば、水溶性で極めて取扱いやすく、優れた消臭機能及び抗菌機能を有する金属フタロシアニン誘導体を素材に担持した消臭抗菌材が提供される。[0001]
[Industrial application fields]
The present invention relates to a deodorizing antibacterial material carrying a novel water-soluble metal phthalocyanine derivative on a material .
[0002]
[Prior art]
Metal phthalocyanine compounds have a structure similar to the active center of metalloenzymes, act as a catalyst with redox ability, have the property of decomposing malodorous substances and converting them into odorless substances, and malodorous substances even in the presence of moisture It has a very advantageous property as a deodorant such as a reaction that exhibits a deodorizing function and a cycle reaction that can effectively use oxygen in the air and has a long catalyst life (for example, JP-B-63). -57063).
[0003]
When these metal phthalocyanine compounds are used as a deodorant, they are generally used after being carried on a material such as fiber or pulp and having a deodorizing function, and then processed into a product. Also, it is preferable that it is easily liquid to water or a solvent because of its handleability. For example, a derivative of carboxylic acid or a sulfonic acid derivative (for example, Inorg. Organomet. Polym., 1991, 1 , 115, J. Mol. Catal., 1981, 10 , 85, J. Mol. Catal., 1988, 44 , 269, etc.). However, these derivatives are hardly soluble as they are, and require treatment such as dissolution using an alkaline aqueous solution, for example, and there is a disadvantage that it is difficult to carry on a material weak against alkali.
[0004]
On the other hand, as a deodorant or antibacterial product in recent years, there are an increasing number of uses that require both functions at the same time rather than a use that requires only a deodorant function or an antibacterial function alone. For such demand, a method of using a deodorant and an antibacterial agent in combination is common. Therefore, if an excellent deodorizing and antibacterial function can be imparted to the material simultaneously with the same compound, the process during industrial production can be greatly omitted, which is preferable.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a metal phthalocyanine derivative and a deodorizing and antibacterial material which are easy to handle due to high solubility in water and have both an excellent deodorizing function and an antibacterial function.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve such problems, the present inventors have sufficiently dissolved in water without using an acid or alkali by introducing a quaternary ammonium base into a metal phthalocyanine compound, It has been found that it not only has an excellent deodorizing function but also has an antibacterial action, and has completed the present invention.
That is, the present invention is an integer of Chemical Formula 2 (wherein m is 0 to 5, n is 2 to 6 (where n is 2, m is 1 to 4), M is a cobalt atom, and X is a bromine atom. The present invention provides a deodorizing antibacterial material in which a water-soluble metal phthalocyanine derivative which is not described in literature is supported on a material.
[0007]
[Chemical 2]

[0008]
The metal phthalocyanine derivatives of the present invention are known in the literature (for example, Chem. Lett., 1991, 1877, Photochem. Photobiol., 1990, 51, 351, J. Heterocycle. Chem., 1981, 18, 1613, etc.) In the formula, n represents an integer of 2 to 6.) A compound represented by Formula 4 (wherein n represents an integer of 2 to 6 and M represents a cobalt atom). It is produced by alkylating this after conversion to.
[0009]
[Chemical 3]

[0010]
[Formula 4]

[0011]
Conversion of the compound represented by Chemical Formula 3 to the compound represented by Chemical Formula 4 is carried out in ammonia-saturated dimethylaminoethanol in the presence of cobalt chloride. The reaction temperature is 150 to 200 ° C., and the reaction time is about 10 to 72 hours. The compound represented by Chemical Formula 4 can be isolated and purified by, for example, alumina column chromatography.
[0012]
Alkylation of the compound represented by Chemical Formula 4 is carried out by reacting with an alkyl halide represented by Chemical Formula 5 (wherein m represents an integer of 0 to 5 and X represents a bromine atom).
[0013]
[Chemical formula 5]

[0014]
Specific examples of the alkyl halide used include methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide and hexyl bromide. Although the reaction is carried out in the presence of a solvent, the solvent used is suitable as long as it does not inhibit the reaction, but dimethylformamide is particularly preferred. The reaction temperature is from room temperature to 100 ° C., and the reaction time is about 5 to 48 hours. After completion of the reaction, the desired product is easily isolated by a conventional method, for example, silica gel column chromatography using dimethylformamide and dimethyl sulfoxide as an elution solvent.
[0015]
In this invention, the deodorizing antibacterial material containing the compound further represented by Chemical formula 2 is provided. The compound represented by Chemical Formula 2 of the present invention is easily dissolved in water as it is, so that a deodorizing and antibacterial function-imparting material such as nonwoven fabric, paper, pulp, etc. is immersed in an aqueous solution of about 1%, and heat fixing. It is possible to easily make a deodorant antibacterial material simply by doing.
[0016]
【Example】
Hereinafter, the present invention will be described in detail with reference to reference examples and examples.
Reference Example 1 4- (2′-dimethylaminoethoxy) phthalonitrile (0.8 g) and anhydrous cobalt chloride (0.24 g) were dissolved in 50 ml of 2-dimethylaminoethanol and reacted at 130 ° C. for 48 hours while bubbling ammonia gas. After completion of the reaction, 200 ml of water was added, adsorbed on an activated alumina column, and eluted with dimethylformamide, thereby tetrakis (2-dimethylaminoethoxy) phthalocyanine cobalt (II), CoPc (O (CH ₂ ) ₂ N (CH _{3 2} ) ₄ was obtained (yield 40%).
¹ H-NMR (DMS0-d6)
δ3.40 (s, 24H), 4.13-5.12 (s, 16H), 7.91-9.40 (m, 12H) UV / VIS (DMF)
λmax = 678,612,348 nm IR (KBr)
1231 cm ⁻¹ (Ar—O—CH ₂ )
Elemental analysis value (as C ₁₂ H ₁₅ N ₃ O)
Calculated value C: 62.13% H: 6.47% N: 18.12% Measured value C: 62.55% H: 5.88% N: 17.76%
[0017]
The obtained tetrakis (2-dimethylaminoethoxy) phthalocyanine cobalt (II) was dissolved in 5 ml of dimethylformamide together with 40-fold mol of methyl iodide and reacted at room temperature for 24 hours. After completion of the reaction, the solvent was concentrated, and the residue was treated with column chromatography (silica gel) to give Compound 1, tetrakis (2-trimethylaminoethoxy) phthalocyanine cobalt (II) iodine salt (m = 0, n = 2) (Yield 68%) was obtained. Compound 1 is dissolved in about 10 g in 1 L of water.
¹ H-NMR (DMS0-d6)
δ3.40 (s, 36H), 4.15-5.18 (s, 16H), 7.98-9.82 (m, 12H) UV / VIS (DMF)
λmax = 678,612,348nm
Elemental analysis (as _{C 52 H 64 N 12 O 4} CoI 4)
Calculated value C: 39.92% H: 4.64% N: 10.75% Measured value C: 41.21% H: 4.25% N: 10.96%
[0018]
Example 1 0.8 g of 4- (2′-dimethylaminoethoxy) phthalonitrile and 0.24 g of anhydrous cobalt chloride were dissolved in 50 ml of 2-dimethylaminoethanol and reacted at 130 ° C. for 48 hours while bubbling ammonia gas. After completion of the reaction, 200 ml of water was added, adsorbed on an activated alumina column, and eluted with dimethylformamide, thereby tetrakis (2-dimethylaminoethoxy) phthalocyanine cobalt (II), CoPc (O (CH ₂ ) ₂ N (CH _{3 2} ) ₄ got.
The resulting tetrakis (2-dimethylaminoethoxy) phthalocyanine cobalt (II) was dissolved in 5 ml of dimethylformamide together with 40 moles of ethyl bromide and reacted at room temperature for 24 hours. After completion of the reaction, the solvent was concentrated, and the residue was treated with column chromatography (silica gel) to obtain Compound 2 (m = 1, n = 2) (yield 35%).
¹ H-NMR (DMS0-d6)
δ1.38 (s, 12H), 3.51 (s, 32H), 4.17-5.22 (s, 16H), 7.96-9.28 (m, 12H)
[0019]
Examples 2 to 4 In Example 1, the same procedure as in Example 1 was conducted except that propyl bromide, butyl bromide and pentyl bromide were used instead of ethyl bromide and the reaction was carried out at 60 ° C. 3-5 (m = 2-4, n = 2) were obtained.
Reference Example 2 Compound 6 (m = 5, n = 2) was carried out in the same manner as in Example 1 except that hexyl bromide was used instead of ethyl bromide and reacted at 60 ° C. in Example 1. Got.
The yields of the obtained compounds 3 to 6 and the results of ¹ H-NMR are shown in Table 1. In Table 1, chemical formula 6 is the following formula (wherein M represents a cobalt atom).
[0020]
[Chemical 6]

[0021]
[Table 1]

[0022]
Example 5 4- (6′-dimethylaminohexyloxy) phthalonitrile (1.0 g) and anhydrous cobalt chloride (0.24 g) were dissolved in 2-dimethylaminoethanol (50 ml) and reacted at 130 ° C. for 48 hours while bubbling ammonia gas. . After completion of the reaction, 200 ml of water was added, adsorbed on an activated alumina column, and eluted with dimethylformamide, whereby tetrakis (6-dimethylaminohexyloxy) phthalocyanine cobalt (II), CoPc (O (CH ₂ ) ₆ N (CH ₃ ) ₂ ) ₄ was obtained (42% yield).
¹ H-NMR (DMS0-d6)
δ3.40 (s, 24H), 4.13-5.12 (s, 64H), 7.91-9.40 (m, 12H) UV / VIS (DMF)
λmax = 678,612,348 nm IR (KBr)
1231 cm ⁻¹ (Ar—O—CH ₂ )
Elemental analysis value (as C ₆₄ H ₈₄ N ₁₂ O ₄ Co)
Calculated value C: 66.72% H: 7.9% N: 14.59% Measured value C: 67.21% H: 8.10% N: 14.45%
[0023]
The obtained tetrakis (6-dimethylaminohexyloxy) phthalocyanine cobalt (II) was dissolved in 5 ml of dimethylformamide together with 40-fold mol of methyl bromide and reacted at room temperature for 24 hours. After completion of the reaction, the solvent was concentrated, and the residue was treated with column chromatography (silica gel) to give compound 7, tetrakis (6-trimethylaminohexyloxy) phthalocyanine cobalt (II) bromine salt (m = 0, n = 6). ) Was obtained (yield 42%).
Elemental analysis value (as C ₆₈ H ₉₆ N ₁₂ O ₄ CoBr ₄ )
Calculated value C: 53.71% H: 6.31% N: 11.06% Measured value C: 52.15% H: 6.81% N: 10.19%
[0024]
Examples 6 to 13 In 20 parts of a 1% aqueous solution of the compounds 1 to 7 obtained in Reference Examples and Examples, a non-woven fabric of acrylic / cotton = 1/1 or 1 part of pulp was soaked and heat-fixed at 90 ° C. The deodorant / antibacterial material was obtained by washing, draining and drying. The resulting deodorant / antibacterial material was evaluated for deodorant / antibacterial effects, and the results are shown in Table 2. The evaluation method is as follows.
[0025]
1. Deodorizing effect measuring method 1 g of the raw material obtained in Examples 6 to 13 was placed in a 3 L desiccator and replaced with bad odor air containing 5 PPM of hydrogen sulfide. After 24 hours, residual odor was confirmed by a sensory test method.
2. Antibacterial effect measurement method (1) Donor bacteria: Bacillus subtilis in culture solution (5 g of peptone, 3 g of meat extract, 10 g of sodium citrate, 20 g of agar dissolved in 1000 ml of water and adjusted to pH 6.5 to 6.6) 35 Culturing was carried out at 1 ° C. for 1 week, and after the spore preparation, the culture solution was heated at 65 ° C. for 30 minutes to obtain a test bacterial solution.
(2) Medium: Sterilized agar medium (prepared by dissolving 10 g of peptone, 5 g of meat extract and 15 g of agar in 1000 ml of water) and a mixture of 20 ml and 0.1 ml of the test bacterial solution, a Petri dish having an inner diameter of about 90 mm The mixture was allowed to stand at room temperature to solidify.
(3) Sample: The material obtained in Examples 6 to 13 was cut into a circle having a diameter of about 9 mm and sterilized to obtain a sample.
(4) Test method: A circular sample was placed on the surface of the medium with tweezers, and allowed to stand at 35 ° C. for 18 hours, and then the transparent zone was observed. Antibacterial activity was judged from the size of the halo part.
[0026]
[Table 2]

[0027]
【The invention's effect】
As described above, according to the present invention, a deodorizing and antibacterial material in which a metal phthalocyanine derivative having an excellent deodorizing function and an antibacterial function is carried on a material is provided.

Claims (1)

It is represented by the following chemical formula 1 (wherein m is 0 to 5, n is 2 to 6 (where n is 2, m is 1 to 4), M is a cobalt atom, and X is a bromine atom). It is the water-soluble phthalocyanine derivative carrying the material, deodorizing antibacterial material.