JPH0948925A - Green dye, process for producing the same, antibacterial deodorant containing the dye, antibacterial deodorant fiber product containing the dye, and process for producing the same - Google Patents

Abstract

(57) Abstract: A natural green dye, a method for producing the same, an antibacterial deodorant containing the dye, an antibacterial deodorant fiber product containing the dye, and a method for producing the same. A dye comprising a metal chlorophyllin derivative represented by the following general formula (1). Embedded image (M = Fe, Cu, Al, Ni, Co, V: R = C
H ₃ , CHO: W _{1 to} W ₃ = H, ammonium, alkali metal)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal chlorophyllin derivative-based dye compound capable of dyeing a textile product in a vivid green color and imparting antibacterial and deodorant properties to the textile product. Regarding The present invention also relates to an antibacterial deodorant comprising the dye compound. The present invention also relates to an antibacterial deodorant fiber product dyed in green with the metal chlorophyllin dye. Further, the present invention is
The present invention relates to a method of converting a chlorophyll compound represented by the general formula (2) contained in leaves of a bamboo genus, which is naturally produced, into a metal chlorophyllin-based dye compound represented by the general formula (1) and collecting the compound. . Furthermore, the present invention relates to a natural green dye comprising the chlorophyllin compound of the general formula (2).

[0002]

2. Description of the Related Art When dyeing fibers such as cotton, silk and wool with a natural dye to a green color, it is said that it is impossible to dye the bright green color of the green leaf itself. . Usually, when dyeing vivid green, the method of first dyeing yellow with Kariyas or Enju and then dyeing the blue of Indigo to green, or the reverse method is common. However, it is difficult to dye a bright green color from green plants in the natural world, and it is particularly difficult to dye a solid green color (“Green Book” Women's University open lecture).

A dull, astringent green color can be dyed by performing a copper mordant, but the structure of the main compound is not clear. Solidago virginia, Enju, mugwort,
Yukari, yamahaze, evening primrose, marigold,
Nemoki and Kariyas also dye green, but the hue is not so good and the fastness is quite poor.
As a commercially available green natural dye, there is "Green Leaf Liquid" manufactured by Tanaka Nao Dye Shoten Co., Ltd. However, it cannot be clearly dyed unless the mordant method is used, and the saturation of the obtained color is limited.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a natural dye obtained from a green plant, particularly a dye capable of green dyeing with a vivid hue and high fastness. is there. The present invention also dyes cotton, silk, wool, etc. in a bright green color, and has antibacterial properties against the fiber,
It is an object of the present invention to provide an antibacterial deodorant natural green dye capable of imparting deodorant properties. Furthermore, the present invention uses a natural dye to produce fibers such as cotton, silk, and wool.
It is an object of the present invention to provide a method for dyeing a green color with a clear hue, high fastness and low cost.

[0005]

[Means for Solving the Problems] As a result of research on dye substances in natural green plants, the present inventors have found that the extract of leaves of the genus Sasa genus, especially the extract of bear bamboo leaves It was found that the contained chlorophyllin compound dyes cotton, silk, wool and the like in a fast and bright green color, and has completed the present invention. As a result of further research, the complexed metal ion of the chlorophyllin compound contained in the extract is replaced with another complexable metal ion, and the substituted metal is alkali-hydrolyzed under heating with the metal ion. Thus, we succeeded in obtaining a stable metal chlorophyllin green dye. Further, as a result of further research, they have found that the chlorophyllin-based or porphyrin-based green dye substances have strong antibacterial and deodorant properties.

Therefore, the present invention that can solve the above problems includes the following inventions. (1) A metal chlorophyllin derivative-based green dye represented by the following general formula (1).

Embedded image (In the formula, R represents a methyl group or a formyl group, M is iron,
Represents a kind of complexing metal ion selected from copper, nickel, aluminum, vanadium and cobalt,
W _{1 to} W ₃ each independently represent one or more kinds of cations selected from hydrogen ion, ammonium ion and alkali metal ion. ).

(2) An antibacterial deodorant containing at least one of the green dyes described in (1) above.

(3) An antibacterial deodorant fiber product which is dyed with the green dye as described in the above item (1).

(4) The antibacterial deodorant fiber product according to item (3), wherein the fiber product is at least one selected from cotton, silk, wool and the like.

(5) A method for producing an antibacterial deodorant fiber product, which comprises dyeing a fiber product with at least one of the green dyes described in (1) above as an acid mordant dye.

(6) The following general formula (2),

Embedded image (In the formula, R represents a methyl group or a formyl group.) Leaves of the bamboo genus Sasa genus containing a chlorophyll compound are selected from iron, copper, nickel, aluminum, vanadium and cobalt. (1) characterized in that it is treated with a compound of at least one metal having the formula (1) to replace magnesium ions with the metal ions, and then the treated leaves are immersed in an alkaline aqueous solution to be heated and hydrolyzed.
A method for producing a metal chlorophyllin derivative-based green dye represented by the general formula (1) according to the item 1.

(7) A green natural dye comprising at least one chlorophyll compound represented by the general formula (2).

(8) An antibacterial deodorant comprising at least one chlorophyllin compound represented by the general formula (2).

(9) An antibacterial deodorant fiber product which is dyed with a green natural dye comprising at least one of the chlorophyll compounds represented by the general formula (2).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The chlorophyll compound represented by the above general formula (2) is a water-insoluble chlorophyll compound contained in bear bamboo leaves, which is extracted by an extraction method using an organic solvent such as acetone. It can be extracted and separated from bamboo grass. However, in order to obtain the metal chlorophyllin derivative-based dye of the general formula (1), other desired metal salts on the acidic side of bear bamboo leaves, for example, metals such as iron, copper, aluminum, nickel, vanadium or cobalt are used. It is effective to add a salt to replace the complexed magnesium ion in the chlorophyll compound of the general formula (2) with the other metal ion described above, and then immerse the treated bear bamboo in an aqueous alkali solution and hydrolyze it by heating. .

[0016] The bear bamboo treatment liquid treated as described above is
Then, solid-liquid separation is performed, and the metal chlorophyllin derivative-based dye-containing liquid of the general formula (1) is collected. The obtained metal chlorophyllin derivative-based dye solution usually has a pH of 12 to 1
3 is a dye solution having a concentration of 0.01 to 5.5%.

In the obtained metal chlorophyllin derivative represented by the above general formula (1), the substituent R is CH ₃ and CH.
It is a mixture of two kinds of metal chlorophyllin derivatives, which is O, and the mixing ratio thereof is CH ₃ : CHO = 1: 1 to 1: 1.
It is in the range of 0.

W _{1 to} W ₃ in the metal chlorophyllin compound represented by the general formula (1) are usually hydrogen atom, ammonium ion or alkali metal atom, and sodium is usually preferred. W _{1 to} W ₃ may be independently sodium, potassium, lithium or the like, or W _{1 to} W ₃ may be present as different alkali metals.

The complexing metal M in the metal chlorophyllin derivative represented by the general formula (1) is magnesium as it is found in the compound of the general formula (2) in a naturally occurring state. Examples of metal ions that replace the magnesium ions include metal ions of iron, copper, nickel, aluminum, vanadium, and cobalt. The complexable metal is particularly preferably a copper or iron ion.

[0020] As the most preferred examples, M is a copper, W ₁ sodium copper chlorophyllin salt to _W-3 is sodium formula (1), M is iron ions, W ₁
˜W ₃ is sodium, iron chlorophyllin sodium salt of the general formula (1), and 9: 1 to 1: 9 mixture of the above two metal chlorophyllin sodium salts.

The stock dye solution containing the metal chlorophyllin derivative represented by the general formula (1), particularly the alkali metal salt thereof, is diluted 10 to 40 times with purified water and adjusted to pH 7 to 9 with a suitable organic acid such as acetic acid. And used as a dyeing solution,
Then, the textile is dyed by boiling by dyeing, and mordanting with an aqueous solution of copper acetate is used to dye the textile.

The metal chlorophyllin derivative represented by the general formula (1) is a compound having antibacterial and deodorant properties as described above. Natural chlorophyll has a deodorant effect than before,
Since it is also known to be highly safe, it is used as an additive in foods such as gum for the purpose of preventing bad breath and toothpaste-related products, and deodorized paper products with chlorophyll attached to pulp fibers and the like. Are known. However, there has been no case where chlorophyll was successfully used as a natural green dye, and there was no case where the deodorizing effect of chlorophyll was applied to textile products such as clothes and bedding.

The metal chlorophyllin alkali metal salt contained in the above general formula (1) is used as a dyeing solution as described above to dye textile products such as cotton, silk and wool to obtain a practical level of fastness. It is possible to obtain a green dyed cloth having a deodorizing effect and a deodorizing effect. For the obtained dyed cloth, ammonia, hydrogen sulfide, methyl mercaptan,
It is possible to confirm the deodorizing effect on acetaldehyde and the like.

[0024]

Embodiments of the present invention will be described below in more detail with reference to each embodiment. However, the present invention is not limited to the following examples.

Example 1 (Production of copper chlorophyllin sodium) Bamboo family Sasa,
27 kg of bear bamboo leaves of the Chimakisasa section are soaked in 290 liters of hot water, 216 g of copper sulfate pentahydrate is added, and the mixture is heated to the boiling point. After boiling, caustic soda 38.5 (w /
v) Add 4 liters of% and continue boiling for 20 minutes. After boiling, take out the bear bamboo grass and wash it thoroughly with water. Then, hot water 8
As described above, the bear-substituted bamboo leaves substituted with copper as described above are put into a boil, 4 liters of 38.5% caustic soda is added, boiled for 90 minutes, and hydrolyzed to extract sodium copper chlorophyllin. Then, solid-liquid separation was performed to obtain an alkaline solution of sodium copper chlorophyllin (concentration = 0.21%; pH = 13.1).

The analytical conditions of the obtained copper chlorophyllin sodium solution by high performance liquid chromatography are as follows, and the obtained results are as shown in the chart of FIG. From this result, it is confirmed that the substituent R in the general formula (1) is R as sodium copper chlorophyllin.
It was found that a mixture of copper chlorophyllin sodium a in which CH ₃ was CH ₃ and copper chlorophyllin sodium b in which the substituent R was CHO was obtained.

[Measurement conditions] HPLC analyzer; Yokogawa HEWLETT PACKAR
D SERIES 1050 detector; UV absorptiometer (measurement wavelength 400 nm) column; YOKOGAWA SIL-C18 / 5B type 4.6 mm in inner diameter, 5 μm in length 15 cm stainless steel tube
Packed with octadecylsilanized silica gel for liquid chromatography column temperature; room temperature

Mobile phase: Phosphoric acid water for liquid chromatography (0.
1 → 100): Methanol solution for liquid chromatography (50:
Starting from 50), after 30 minutes, gradation is applied so that a phosphoric acid water for liquid chromatography (0.1 → 100): methanol mixed liquid for liquid chromatography (0: 100) is obtained. Flow rate: 1 ml / min Detection sensitivity: The peak height of copper chlorophyllin sodium obtained from 20 μl of the sample solution is adjusted to be 2 to 5 cm.

[Results] See chart. The retention time of copper chlorophyllin sodium a is about 25 minutes,
The retention time of copper chlorophyllin sodium b was about 29 minutes.

Example 2 (Production of iron chlorophyllin sodium) In Example 1, the same bear bamboo as that used in the production of copper chlorophyllin sodium was used as a raw material, and copper sulfate.5 was used as a metal compound for a substituted metal ion. 250 g of ferrous sulfate was used instead of 216 g of hydrate, the same metal ion substitution reaction as in Example 1 and the extraction and recovery method of the produced iron chlorophyllin sodium salt were carried out to obtain iron chlorophyllin sodium salt. .

The conditions for high performance liquid chromatography analysis of the obtained sodium iron chlorophyllin are as follows, and the obtained analysis results are as shown in the chart of FIG. From FIG. 2, it was found that as iron chlorophyllin sodium, a mixture of iron chlorophyllin sodium a in which the substituent R in the general formula (1) was CH ₃ and iron chlorophyllin sodium b in which the substituent R was CHO was obtained. found.

[Measurement conditions] HPLC analyzer; Yokogawa HEWLETT PACKAR
D SERIES 1050 detector; UV absorptiometer (measurement wavelength 400 nm) column; YOKOGAWA SIL-C18 / 5B type 4.6 mm in inner diameter, 5 μm in length 15 cm stainless steel tube
Packed with octadecylsilanized silica gel for liquid chromatography column temperature; room temperature

Mobile phase: Phosphoric acid water for liquid chromatography (0.
1 → 100): Methanol solution for liquid chromatography (50:
Starting from 50), after 30 minutes, gradation is applied so that a phosphoric acid water for liquid chromatography (0.1 → 100): methanol mixed liquid for liquid chromatography (0: 100) is obtained. Flow rate: 1 ml / min Detection sensitivity: Adjust so that the peak height of sodium iron chlorophyllin obtained from 20 μl of the sample solution is 2 to 10 cm.

[Results] See chart. The retention time of iron chlorophyllin sodium a is about 24 minutes,
The retention time of iron chlorophyllin sodium b was about 20 minutes.

Example 3 (Dyeing of Cotton Cloth) Cotton cloth was cationized in advance by the following method and used for dyeing. Cathionone UK (manufactured by Yatasha Yushi Kogyo Co., Ltd.) 2% aqueous solution sodium hydroxide 0.4% aqueous solution Treated at a bath ratio of 1:20 at 80 ° C for 60 minutes.

The copper chlorophyllin sodium extract obtained in Example 1 was diluted 10 times with water to prepare two kinds of dyeing solutions having pH adjusted to 8 and 9. The dyeing method is as follows: cationized cotton cloth is simmered for 20 minutes at a bath ratio of 1:40, and then one is treated with a 2% copper acetate solution at a bath ratio of 1:40 for 20 minutes and then post-treated (mordanting). The method of rinsing with water and natural drying was adopted, and the other method of rinsing was followed by direct rinsing with water and natural drying without post-treatment. 3% as soaping agent o. w. f. (On weight of fiber)
Marcel soap (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used.
The results are shown in Tables 1 and 2.

[0037]

[Table 1] <Hue>

[0038]

[Table 2]

Measuring method: Measuring instrument: Color difference meter CR-100 (Minolta Camera Sales Co., Ltd.) Light source: D65 Number of measurements; L ^* a ^* b ^* Average value of three different colorimetric systems. The Munsell color system is a value measured at one location.

Dyeing fastness: The dyed cotton cloth was post-treated with 2% copper acetate and dried on the sun. The results are shown in Table 3. Fastness test method: light fastness; JIS L 0842 carbon arc lamp method washing fastness; JIS L 0844 A-1 No. sweat fastness; JIS L 0848 A method friction fastness; JIS L 0849 II type

[0041]

[Table 3]

Comparative Example 1 A cationic cotton cloth treated in the same manner as in Example 1 was dyed with the following dyes to determine and measure the hue and dye fastness. The results are shown in Table 4. 1. Commercially available natural dye: "Green leaf liquor" (manufactured by Tanaka Nao Shoten, chemical structure unknown), no pH adjustment during dyeing Post-treatment with 2% copper acetate. 2. a. As a direct dye, Kayarus Cupro Green G (Col
or Index Direct Green 59) was used. b. As an acid dye, Kayanol Milling Green 5GW (Col
or Index Acid Green 28) was used.

[0043]

[Table 4]

[0044]

[Table 5] Note 1: Dye density is the density to fabric weight Note 2: Numerical value is the actual measurement value

From the results of Example 3 and Comparative Example 1, the following can be said in dyeing the cationized cotton cloth. 1. Regarding the hue, the copper chlorophyllin sodium dye obtained in Example 1 is clearer than the dye of Comparative Example 1 and is excellent as a green dye, and has high practical value. In addition, the dye of Example 1 is superior to the C * value in terms of saturation even when compared with the natural dye “green leaf liquor”. L * a
In * b * color system, the saturation is

[Equation 1] And comparing the green dye of Example 1 with “green leaf liquor” which is a natural green dye, C of the green dye of Example 1
* You can see that the value is high. 2. Regarding the fastness, it can be confirmed that the green dye of Example 1 is relatively excellent and has sufficient practicality.

Example 4 Dyeing of silk cloth: Using the copper chlorophyllin sodium dye obtained by the production method of Example 1, dyeing of silk cloth was carried out according to the same dyeing method as in Example 3 without post-treatment. The hue and fastness were judged and measured. 3% as soaping agent o. w. f. Monogen (Daiichi Kogyo Seiyaku Co., Ltd.) was used. The results are shown in Tables 6 and 7.

[0047]

[Table 6]

[0048]

[Table 7]

Comparative Example 2 Using the same silk cloth as in Example 4, dyeing was performed in the same manner as in Comparative Example 1. However, 10 g per 1 g of silk cloth
Staining was performed after adding g of acetic acid. The hue measurement results are shown in Table 8, and the dyeing fastness evaluation results are shown in Table 9.

[0050]

[Table 8]

[0051]

[Table 9] Note 1: Dye density is the density with respect to the fabric weight Note 2: The value at 0.4% is the measured value, and the value at 2.0% is “Silk dyeing sample” (June 20, 1989 Nippon Kayaku Co., Ltd. ) Edited / produced)

From Example 4 and Comparative Example 2, in dyeing silk cloth, Regarding the hue, it is clear from the comparison of the C * value with "green leaf liquor" which is a natural green dye that the dye of Example 4 gives a clearer green color than the dyes of Comparative Example 2. . 2. As for the fastness, it can be seen that the dye of Example 4 is relatively excellent, and particularly the fastness to washing and the fastness to rubbing are remarkably excellent.

Example 5 Wool Dyeing: Using the dyestuff prepared in Example 1, dyeing wool according to the same dyeing procedure as in Example 3,
The hue and fastness were measured and judged. 3% as soaping agent o. w. f. Monogen (Daiichi Kogyo Seiyaku Co., Ltd.) was used. The results are shown in Tables 10 and 11. Table 1
From 0 and Table 11, it can be seen that the green dye of Example 1 exhibits excellent hue and fastness even in dyeing wool.

[0054]

[Table 10]

[0055]

[Table 11]

Example 6 Sodium iron chlorophyllin obtained in Example 2 was added to
A dye solution having a pH of 12.8 containing 025% was adjusted to pH 9.2, and the silk cloth was boiled and dyed at a bath ratio of 1:40 for 20 minutes, washed with water without mordant, and naturally dried to obtain a dyed silk cloth. The results are shown in Table 12.

Lightfastness: JIS L 0842 Carbon Arc Light Method Washing Fastness: JIS L 0844 A-1 Dry Cleaning: JIS L 0860 Mixed Weaving
No. A Sweat fastness: JIS L 0848 A method Friction fastness: JIS L 0849 II type hot pressing: JIS L 0850 A method

[Table 12]

Example 7 Antibacterial test of natural green dyes prepared in Example 1: Cotton cloth dyed according to Examples 3 and 4 using the copper chlorophyllin sodium dye prepared in Example 1. Also, the silk cloth was tested and evaluated by the bacterial count method, which is an antibacterial processing evaluation test method of the Textile Products Sanitary Processing Council. At the same time, undyed cotton cloth and silk cloth, cotton cloth and silk cloth dyed with the commercially available natural dye “Green Leaf Liquid” (manufactured by Tanaka Nao Shoten Co., Ltd., chemical structure unknown), synthetic acid dye (Ka
yanol Milling Green 5GW (Color Index Acid Green 2
A comparative test was carried out using the cotton cloth and silk cloth dyed in 8).

This method is a method in which the antibacterial processed sample and the unprocessed sample are compared and measured as an increase / decrease value or a difference in the increase / decrease value under conditions close to when worn. Staphylococcus aurcus as a test bacterium
IFO 12732), 0.2 ml of sterilized sample cloth, 0.2 ml of broth suspension of test bacteria adjusted so that the number of bacteria is 5 to 30 x 10 ⁵ cells / ml, and sealed container After culturing at 37 ° C. for 18 hours, the viable cell count was measured to determine the increase / decrease value relative to the inoculum count. The test results are shown in Tables 13 and 14. In this test, if the increase / decrease value is 1.6 times or more,
It is recognized that it has an antibacterial effect in practice.

[0060]

[Table 13] logA-logB = 3.4> 2 ... Test is effective Increase / decrease value = logC-logA Increase / decrease value difference = (logB-logA)-(logC-
logA) (* 1) Testing organization: Japan Spinning Inspection Association Testing Center

[0061]

[Table 14] Results of antibacterial test by bacterial count method ─────────────────────────────────── Number logC Increase / decrease value Increase / decrease difference value ─────────────────────────────────── Undyed silk cloth 7.7 2 .3 1.1 ──────────────────────────────── Bear Bamboo Leaf Extract Liquid Dye Cloth 3.3-2. 1 5.5 Silk ──────────────────────────────── Green leaf liquor dyed cloth 3.6-1.8 5. 2 ──────────────────────────────── Synthetic acid dye fabric 8.3 2.9 0.5 ─── ──────────────────────────────── Undyed cotton cloth 8.2 2.8 0.6 ─── ──────────────────────────── Bear Bamboo Leaf Extract Liquid Dye Cloth 3.8 1.6 5.0 Cotton ───── ─────────────────────────── Green leaf liquor dyed cloth 5.7 0.3 3.1 ─────────── ────────────────────── Synthetic acid dye dyeing cloth 7.9 2.5 0.9 ────────────── ─────────────────────

From the above Tables 13 and 14, the undyed cotton cloth and silk cloth, and the synthetic acid dye-dyed cotton cloth and silk cloth were found to grow in fungi with respect to the number of inoculated cells, but the bear of Example 1 of the present invention was used. The cloth dyed with the bamboo extract dye inhibits the growth of 10 ⁴ to 10 ⁵ bacteria, and the difference between the increase and decrease of cotton cloth and silk cloth is 5.5, 5.0 and 1.6 or more, respectively, which indicates that the antibacterial effect is obtained. It is observed that the usefulness of the bear bamboo extract of the present invention is clear.

Example 8 Antibacterial test by washing treatment bacteria count method: The sample used in Example 7 was subjected to an antibacterial test by the laundry treatment bacteria count method, which is an antibacterial treatment test method of the Textile Products Hygiene Processing Council, evaluated. This method uses a 0.2% cleaning solution (liquid temperature 40 ° C),
Washing with a washing machine is performed for 5 to 6 minutes under the condition of a bath ratio of 1:30, and then the sample is dehydrated, followed by rinsing for 2 to 3 minutes or rinsing with water. This is a test method in which the above washing and rinsing processes are repeated 10 times, and the washing treatment is carried out by drying in the shade or using a dryer at 80 ° C. or lower, and the sample after the washing treatment is based on the bacteria measurement method of Example 6. Then, the increase / decrease value with respect to the number of inoculated cells was obtained to evaluate the practical antibacterial effect.
The tests are shown in Tables 15 and 16.

[0064]

[Table 15] logA-logB = 3.4> 2 ... Test is effective Increase / decrease value = logC-logA Increase / decrease value difference = (logB-logA)-(logC-
logA)

[0065]

[Table 16] Results of antibacterial test by 10-wash treatment bacteria count method ─────────────────────────────────── ─ Sample number of bacteria logC Increase / decrease value Increase / decrease difference ──────────────────────────────────── Undyed silk cloth 3.8-1.5 4.9 ──────────────────────────────── Bear Bamboo Leaf Extract Liquid Dye Cloth 4 -9-0.4 3.8 Silk ──────────────────────────────── Green leaf liquor dyeing cloth 5.60 3.3 3.1 ──────────────────────────────── Synthetic acid dye dyeing cloth 5.2-0.1 3 . 5 ─────────────────────────────────── Undyed cotton cloth 5.8 0. 2.9 ──────────────────────────────── Bear Bamboo Leaf Extract Liquid Dye Cloth 4.0-1.34 .7 Cotton ──────────────────────────────── Green leaf liquor dyed cloth 5.3 0 3.4 ───── ──────────────────────────── Synthetic acid dye dyeing cloth 3.3-2.0 5.4 ──────── ────────────────────────────

From the above Tables 15 and 16, the cotton cloth and silk cloth dyed with the bear bamboo leaf extract dye were compared with the unprocessed cloth,
It suppresses the growth of 10 ⁴ bacteria, and the difference in increase / decrease value is 3.
It was 8, 4.7 and 1.6 or more, and it is recognized that it has an antibacterial effect. Compared with the results of Example 6, the bacterial treatment of the undyed cotton cloth and silk cloth, the synthetic acid dye-dyed cotton cloth and the silk cloth was improved by the washing treatment, because the sodium linear alkylsulfonate in the detergent used It is considered that there was an effect of the bactericidal action.

Example 9 Deodorization test: The cotton cloth, silk cloth and wool dyed in Examples 3 to 5 are ammonia, in comparison with untreated cloth,
The deodorizing ability imparting effect was measured and evaluated using hydrogen sulfide, methyl mercaptan, and acetaldehyde. Put 1 g of sample cloth in each vial tube and seal it with a syringe, and use a syringe to smell ammonia (1000 ppm concentration), hydrogen sulfide (100 ppm concentration), methyl mercaptan (70 p
pm concentration) and acetaldehyde (300 ppm concentration) are respectively injected, and after 10 minutes, the concentration of each malodorous gas in the vial tube is measured. The results are shown in Table 17 as the malodorous gas removal rate after 10 minutes.

[0068]

[Table 17] * The following are the natural materials used in each deodorant test.・ Cotton: Kanakin No. 3 ・ Silk: Plain weave white cloth for JIS fastness test (with 14 stitches) ・ Wool: Yarn for dyeing 48/2

From Table 17, it can be seen that ammonia has a small difference in the removal rate between the dyed cloth and the unprocessed cloth (undyed cloth) by the bear bamboo extract liquid dye because ammonia is easily adsorbed on the fiber material itself. A remarkable effect was confirmed for cotton cloth and silk cloth. However, in wool, the deodorizing effect due to the dyeing of the bear bamboo extract dye has not been remarkably exhibited. Due to the structure of wool fiber, it is presumed that the reason is that the adsorption site of ammonia is somewhat blocked by the dye. Although the removal rate for sulfur compounds such as hydrogen sulfide and methyl mercaptan is inferior to that for ammonia, the deodorizing effect of the bear bamboo extract liquid dye is remarkable because it is difficult to be adsorbed by the fiber material itself. It is speculated that the difference in the effect due to these malodorous substances is due to the different deodorant mechanism.

Further, when the odor of the sample cloth after absorbing the malodor was sensory measured, it was confirmed that the unstained cloth had the unsatisfactory odor. However, in the cloth stained with the bear bamboo extract, the unstained odor was found. There wasn't. It is presumed that the malodorous substance was decomposed after adsorption by the bear bamboo extract dye.

[0071]

As described in detail above, according to the present invention,
It is possible to provide a metal chlorophyllin derivative, which is a natural dye capable of dyeing fibers such as cotton, silk, and wool with a fast and inexpensive color in a vivid green color. In addition, by dyeing a fiber product particularly using a metal chlorophyllin alkali metal salt, it is possible to provide a green dyed fiber product having excellent antibacterial properties and deodorant properties.

[Brief description of drawings]

FIG. 1 is an HPLC analysis chart of copper chlorophyllin sodium.

FIG. 2 is a HPLC analysis chart of sodium iron chlorophyllin.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A61L 2/16 A61L 2/16 Z 9/01 9/01 K C07D 487/22 9271-4C C07D 487 / 22 C09B 61/00 C09B 61/00 B D06P 1/34 D06P 1/34 1/36 1/36 A D21H 21/30 D21H 3/80 (72) Inventor Isamu Harashima 4-617 Umego, Ome-shi, Tokyo 1 (72) Inventor Nobuyoshi Sato 5931-70 Izumino, Chino City, Nagano Prefecture (72) Inventor Seiichi Horikawa 2265 A-102, Shimadzu, Matsumoto City, Nagano Prefecture A-102 (72) Takaaki Oizumi Nijigaoka, Aso-ku, Kawasaki City, Kanagawa Prefecture 2-3, 11-603

Claims (7)

[Claims] 1. A metal chlorophyllin derivative-based green dye represented by the following general formula (1). Embedded image (In the formula, R represents a methyl group or a formyl group, M is iron,
Represents a metal ion having a complexing ability selected from copper, nickel, aluminum, cobalt and vanadium, and W ₁ to
W ₃ represents one or more kinds of cations selected from the group consisting of hydrogen ion, ammonium ion and alkali metal ion. ). 2. An antibacterial deodorant containing at least one of the green dyes according to claim 1. 3. An antibacterial deodorant fiber product, which is dyed with the green dye according to claim 1. 4. The antibacterial deodorant fiber product according to claim 3, wherein the fiber product is made of at least one selected from cotton, silk, wool and the like. 5. A method for producing an antibacterial deodorant textile product, which comprises dyeing a textile product with at least one of the green dyes according to claim 1 as an acid mordant dye. 6. The following general formula (2): (In the formula, R represents a methyl group or a formyl group.) A leaf of the bamboo genus Bamboo family containing a chlorophyll compound is selected from iron, copper, nickel, aluminum, cobalt and vanadium. 2. The general formula (1) according to claim 1, characterized in that magnesium ions are replaced with the metal ions by treating with a compound of at least one metal having, and then the treated leaves are heated and hydrolyzed with an alkaline aqueous solution and extracted. A method for producing a metal chlorophyllin derivative-based green dye represented by 1). 7. A green natural dye comprising a chlorophyll compound represented by the general formula (2).