JP3421737B2 - Antibacterial dyestuff and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial dyeing product and a method for producing the same, and in particular, by dyeing a polymer material with a dye containing an antibacterial metal, or by dyeing the polymer material with an antibacterial metal. The present invention relates to an antibacterial dyeing product having a dyeing function and an antibacterial function at the same time, which is obtained by acting as a mordant, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, for dyeing a polymer material and imparting an antibacterial function, a composition containing a fine powder zeolite containing an antibacterial metal ion as an active ingredient after dyeing by a known method. The method of spraying is used. Also,
After dyeing, there is also a method of kneading a zeolite carrying an antibacterial metal into the dyed product. As described above, conventionally, in order to obtain an antibacterial dyeing product, a two-step processing process of performing an antibacterial property imparting process in another process after the dyeing process has been performed.

On the other hand, a metal-containing dye is known as a dye containing a metal. This metal-containing dye is characterized in that the dye can be surely adsorbed inside the fiber, but when dyeing animal protein fibers such as silk thread, there are some difficulties in the vividness of the color after dyeing. However, gold-containing dyes have not been widely used in practice. Such dyeing properties produced by the metallized dyes are associated with the high molecular weight of the metallized dyes. Therefore, although various metal-containing dyes containing metals have already been commercialized, there is still no idea to adsorb this dye to a polymer material to produce a dyed product having an antibacterial function.

There is also known a technique in which a polymer material is first dyed with a dye containing no metal, and then the metal acts as a mordant, and this technique is used to impart an antibacterial function to the dyed product. I still have no idea.

[0005]

The dyeing process is a processing operation in which a dye is used to permeate and fix a dye in a material. Generally, disperse dyes are mainly used for synthetic fibers including three major synthetic fibers of polyester, polyamide and polyacrylic, and rayon fibers, acetate fibers and other cellulose fibers are direct dyes, vat dyes, sulfur dyes, naphthol dyes, and reactive dyes. Is mainly used. Acid dyes and acid mordant dyes are mainly used as dyes for animal protein fibers such as silk and wool. Normally, the dyeing process is completed by immersing the material in a dyeing solution containing a dye and a dyeing aid such as a dyeing accelerator (or leveling agent) for accelerating dyeing, heating or printing, and then steaming. . In the conventional dyeing process, the main purpose was to develop vivid colors by adsorbing and fixing the dye in the dyeing process through the work of dyeing the material, but in recent years, let's add functions other than coloring at the same time. The development of such technology has become an important theme from a practical point of view.

Although a technique for dyeing a polymer material with a metal-containing dye is known, a satisfactory method for adsorbing a large amount of dye on the polymer material has not been disclosed yet. Usually, in order to adsorb a large amount of dye, a method of increasing the adsorbed amount of the dye by increasing the dyeing temperature or dyeing time is adopted. However, there is a problem that it is not appropriate to react a natural polymer material in a high temperature / high pressure atmosphere in the presence of water for a long time because mechanical properties such as strength and elongation of the natural polymer material are deteriorated. . Further, when dyeing by a usual method, there is a problem that the dye once introduced is likely to be eluted even though the dye can be introduced into the material.

[0007] Therefore, the development of a technique that enables dyeing and imparting an antibacterial function at the same time in one process consisting of dyeing a polymeric material with a metal-containing dye and adsorbing a large amount of the dye onto the material. It has been strongly desired that the dyeing product having an antibacterial function can be efficiently and economically produced by this technique.

The present invention is intended to solve the above-mentioned problems. By dyeing a polymer material with an antibacterial metal-containing dye, the dye has good dyeing and useful antibacterial properties at the same time, and has excellent wash resistance. It is an object of the present invention to provide a method for producing an antibacterial dyeing product which also has the property of stable antibacterial property and the obtained antibacterial dyeing product.

[0009]

Means for Solving the Problems The inventors of the present invention have made earnest studies on the production of a polymer material having good dyeing and useful antibacterial properties only in a dyeing step. As a result, a neutral salt aqueous solution and an alkaline aqueous solution have been obtained. For the first time, it has been found that pretreatment of a polymer material with an aqueous chitosan solution allows the material to be dyed by dyeing with a metal-containing dye (metal-containing dye), and at the same time imparts an antibacterial function. It came to completion.

The antibacterial dye of the present invention is calcium chloride
Arm, potassium chloride, calcium nitrate, lithium bromide, sodium hydroxide, potassium hydroxide, potassium carbonate, aqueous solution of a compound selected from potassium nitrate and sodium nitrate, or is pretreated by immersion processing in the aqueous chitosan solution, the antimicrobial metal Dyeing with a dye contained, natural material selected from silk and wool, cellulose fiber selected from rayon and acetate, or acrylic,
Made of high polymer material that is a synthetic fiber selected from vinylon and nylon, or calcium chloride, potassium chloride
Dye which is pretreated by dipping process with an aqueous solution of a compound selected from sodium, calcium nitrate, lithium bromide , sodium hydroxide, potassium hydroxide, potassium carbonate, potassium nitrate and sodium nitrate, or an aqueous chitosan solution, and contains no antibacterial metal. A polymer material, which is a cellulose fiber selected from rayon and acetate or a synthetic fiber selected from acryl, vinylon and nylon, which is dyed with, is treated with an antibacterial metal mordant. In the present specification, the above-mentioned calci chloride is used.
Um, potassium chloride, calcium nitrate, and lithiated bromide
A compound selected from Um is referred to as a neutral salt for convenience of explanation.
You As the dye containing no antibacterial metal, a known chemically synthesized dye may be used, or a so-called “vegetation dye” using a plant-derived dye may be used. As the antibacterial metal mordant, a mordant containing a metal used for coloring is used.

The method for producing an antibacterial dyed product of the present invention is a silk cloth.
And natural materials selected from wool and wool, rayon and acete
Cellulose fibers selected from
High content, which is a synthetic fiber selected from Nilon and Nylon
The child material is neutral salt solution, sodium hydroxide,
Lithium, potassium carbonate, potassium nitrate and sodium nitrate
An aqueous solution of inorganic alkali selected from um, or chitosa
Pretreatment by dipping in an aqueous solution of water and then antibacterial metal
Consisting of obtaining a dyed product by dyeing with a dye containing
Alternatively, a cell selected from rayon and acetate
Loin fiber or acrylic, vinylon and nylon
A synthetic polymeric material selected from
Liquid, sodium hydroxide, potassium hydroxide, potassium carbonate
None selected from aluminum, potassium nitrate and sodium nitrate
Dipping in alkaline machine or chitosan solution
Pre-treated with this, the pre-treated polymer material is antibacterial
Dyeing products obtained by dyeing with a dye containing no metal
Is it possible to obtain a dyed product by applying an antibacterial metal mordant to it?
Consists of This makes it possible to economically and effectively obtain an antibacterial material having a vivid color tone and a function of suppressing an increase in pathogenic bacteria.

[0012] The concentration of the above Symbol neutral aqueous salt solution 1.35~1.50g / cm
³ , the concentration of the inorganic alkaline aqueous solution is 0.2 to 0.8%, and the concentration of the chitosan aqueous solution is preferably 5 to 20 g / L. The above-mentioned natural materials include silk protein such as silk fibroin and silk sericin produced by silkworm, and animal protein fiber composed of wool keratin. When the polymer material is silk thread, the pretreatment process with the neutral salt aqueous solution reduces the molecular orientation degree of silk thread to 75% or less, and the dyeing rate is 10%.
It is preferable to carry out as described above. A silk fibroin film can also be used as the natural material.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As a polymer material that can be used in the present invention, molecules of an antibacterial dye are adsorbed and diffused and enter the inside of a polymer material.
There is no particular limitation as long as the physical / chemical interaction is enhanced by taking a covalent bond, a hydrophobic bond, or an ionic bond. As a polymer material composed of an organic polymer that can be used, as a fiber form, animal protein fiber as described above,
There are natural cellulose fibers, synthetic fibers, and fiber products thereof. Among these materials, animal protein fibers are the most effective and can be conveniently used. The form of the polymer material is not particularly limited, and includes yarn, cloth (woven fabric, knitted fabric, etc.), non-woven fabric, fiber aggregate and the like. Further, the form of the material also includes a film form, for example, a silk fibroin membrane prepared from a silk fibroin aqueous solution obtained by dissolving silk fibroin fiber in an aqueous solution of a neutral salt such as lithium bromide and dialysis. Is also included.

The pretreatment of the polymer material performed in the present invention is for adsorbing a large amount of dye on the material,
As described above, (1) immersion treatment with a neutral salt aqueous solution, (2)
There are dipping treatment with alkaline aqueous solution and (3) pad-dry-cure treatment with aqueous chitosan solution. These processes will be described below.

(1) In the present invention, any known neutral salt can be used without particular limitation as a treating agent used in the immersion treatment of the aqueous solution of the neutral salt for increasing the adsorption amount of the metal-containing dye. For example, calcium chloride, potassium chloride , nitrate
Known neutral salts such as lucium and lithium bromide can be used. Hereinafter, a silk thread will be described as an example of the polymer material.

The concentration of the neutral salt aqueous solution is usually 1.35 to 1.50 g / cm ³ , preferably 1.38 to 1, measured with a Baume standard pycnometer.
It is 1.49 g / cm ³ . If the neutral salt concentration is less than 1.35 g / cm ³ , the silk shrinkage of silk is not sufficient even if heated, and it is uneconomical.
If it exceeds 1.50 g / cm ³ , the silk thread shrinks in a short time even if the heating temperature is low, and it becomes difficult to control the salt shrinkage rate. Here, the salt shrinkage refers to a phenomenon in which the fibers shrink in the lengthwise direction due to the heat treatment. The heat treatment may be carried out at 65 ° C. to 95 ° C., and the treatment time may be appropriately adjusted while observing the shrinkage state of the silk thread, but generally 1 minute to 30 minutes is convenient. After the salt contraction reaction, it is necessary to wash with a large amount of running water to sufficiently remove the neutral salt component contained in the silk thread. Otherwise, the neutral salt reacts with the dye in the dyeing step to cause precipitation, which tends to cause uneven dyeing, resulting in a decrease in dyeing efficiency. By dipping the silk thread in a neutral salt solution, the silk thread shrinks, and the molecular orientation of silk fibroin decreases during this process.

By dipping the silk yarn with an aqueous solution of a neutral salt to increase the amount of dye adsorbed, the degree of molecular orientation can be lowered to 75% or less, and the dye adsorption rate of 10% can be obtained by this pretreatment. The above can be done.

As described above, when the silk yarn is heat-treated with the neutral salt aqueous solution, the silk yarn shrinks in the length direction. In such salt shrinkage, the salt shrinkage ratio can be controlled by the concentration of the neutral salt, the treatment temperature and the treatment time. Neutral salt concentration is measured with a Baume standard hydrometer. Preferred concentrations are, for example, 1.38 to 1.49 g / cm ³ for calcium nitrate, most preferred concentrations are 1.41 to 1.43 g / cm ³ . If the concentration is less than 1.38 g / cm ³ , the salt contraction effect is not sufficient, and if the concentration exceeds 1.49 g / cm ³ , the salt contraction becomes insufficient on the contrary. If the treatment temperature is 80 ° C and the calcium nitrate concentration is 1.41 g / cm ³ , the treatment time is 3
At 0 seconds, 1 minute, and 2 minutes, the salt reduction rates are 4%, 12%, and 22%, respectively. If the calcium nitrate concentration is 1.43 g / cm ³ , the treatment time is 30 seconds, 1 minute, and 2 minutes, and the salt reduction ratios are 13%, 22%, and 43%, respectively.
%, And if the calcium nitrate concentration is 1.49 g / cm ³ , the salt shrinkage ratios are 25%, 33%, and 53%, respectively, in the same treatment time.

The conditions for the salt shrinkage ratio to reach an equilibrium state are:
With a calcium nitrate concentration of 1.49 g / cm ³ for 1 minute treatment,
The treatment temperature is 70 ℃ and 90 ℃, and the salt shrinkage is 25% and 72%, respectively.
%.

(2) In the present invention, any known alkaline reagent can be used without particular limitation as the treating agent used in the immersion treatment of the alkaline aqueous solution for increasing the adsorption amount of the metal-containing dye. For example, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium nitrate, sodium nitrate and the like can be similarly used. Alkali treatment chemical concentration is 0.2 ~
If it is less than this lower limit, the effect of the alkali treatment does not appear, and if it is more than this upper limit, hydrolysis of the silk thread occurs due to the alkaline chemical, and the mechanical properties of the obtained product deteriorate. The alkaline chemical treatment deteriorates the mechanical properties of the polymer material to some extent. In order to reduce this degree of deterioration, for example, in the case of silk thread, the silk thread is immersed in an alkaline aqueous solution of a specified concentration (0.6%) for 20 minutes at room temperature, the pick up rate is set to 50-150%, and the After placing in a container and sealing, put in a thermostat at 30 ° C and let stand for 24 hours.

(3) In the pretreatment with the chitosan aqueous solution used for increasing the adsorption amount of the metal-containing dye in the present invention, the polymer material is immersed in the chitosan aqueous solution in which the chitosan is dissolved in the acetic acid aqueous solution, and then the pad-dry-cure is performed. Processed by law.
The polymer material is immersed in an aqueous solution of chitosan solubilized with an aqueous solution of acetic acid and dried. The acetic acid aqueous solution concentration and the chitosan aqueous solution concentration are preferably 1 to 5 mL / L and 5 to 20 g / L, respectively. Drying temperature is 90 ℃ -160 ℃, drying time is 1-30
Minutes are preferred.

The metal-containing dye (metal-containing dye) that can be used in the present invention is not particularly limited, but for example, the following 1:
Mention may be made of type 1 metal complex dyes and 1: 2 metal complex dyes.

1: 1 type metal complex salt dye: a dye in which one metal atom is coordinated to one molecule of a dye having a sulfonic acid group. For example, as Neolan developed by Chiba, Neolan: Black AL
U, Black 2G, Black WA, BlackWA Extra N, Blue FR, Blue
There are 2G, Blue 2R, Blue 3R, Bordeaux BE, BM, RM, Brown TCN, etc.Also, as Palatine Fast developed by IG, Palat
ine Fast: Black RRN, Black SAN, Black WAN, Blue BN, Bl
ue GGN, Blue GGNA, Bordeaux RN, Brown BRRN etc.
Also, Kayakalan Bordeau BL, Kayakalan Brown GL, Kaya
kalan Gray BL167, Kayakalan Yellow GL, Kayalax Yello
w G, Kayakalan Black 2RL, KayakalanBlackBGL, Kayakala
n Orange RL etc.

1: 2 type metal complex salt dye: A dye in which two molecules of a dye containing a sulfonamide group, a methylsulfone group or the like instead of a sulfonic acid group are coordinate-bonded to one metal atom.
For example, Irgalan (Gy), Cibalan (Chiba), Landsyn (Sando
z), Isolan (FBY), etc. These dyes are characterized by excellent dyeability and fastness.

In addition to the above, many gold-containing dyes such as Irga
lan Yellow 2GL, Lanacron Navy Blue B, Kayarus Supra
Rubine BL and Kayarus Tug. Blue GL can be used.

The metal contained in the dye is preferably a metal having antibacterial properties such as chromium, cobalt, zinc and copper. A dye containing chromium metal is particularly preferable for stably imparting an excellent antibacterial function to, for example, animal protein fibers. The dyeing with the metal-containing dye in the present invention is carried out by immersing the polymeric material in 0 to 2% owf of ammonium acetate as a dyeing aid for 5 to 15 minutes, then adding 0.5 to 2% owf of the metal-containing dye, and further immersing it. It is done by doing. Thereafter, the temperature of the dyeing bath is gradually raised to 90 ° C. over 50 to 60 minutes, and dyeing is performed at the target temperature for 60 minutes.

Further, as a technique capable of imparting an antibacterial function to a polymer material, which can be used in the present invention, there is also a technique of treating with a mordant containing an antibacterial metal after dyeing with a dye containing no antibacterial metal. . This technique is a type of dyeing in which a dye molecule and a metal form a coordinate bond during dyeing, which is a so-called mordant dye. In this case, the type of dye actually used is not particularly limited,
Dyes which can be mordanted by using chromium as a mordant in the post-treatment and serious direct dyes which can be subjected to the copper-containing fix treatment in the post-treatment are preferable. The copper-containing fix treatment is a treatment with a fixing agent containing copper, which is performed to improve the dyeing fastness. Acid dyes that can be mordanted with chromium are called acid mordants or chrome dyes,
(1) After dyeing, chromium is treated with a dilute aqueous solution of potassium dichromate, etc. to treat it with chromium, or (2) metachromic method that simultaneously dyes and treats chromium. However, it is possible to dye with two types of acid mordant dyes. By this method, extremely excellent light resistance and wet fastness (wash fastness) can be obtained, and thus it is particularly suitable for silk and wool. Most of the serious direct dyes are copper-containing azo dyes. As a specific dye,
Sirius (As a manufacturer, Anil, ByDB, FBy, FIVC, VC
Etc.).

[0028]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The antibacterial activity evaluation methods and physical property evaluation methods performed in the following Examples and Comparative Examples are as follows.

(1) As a phytopathogenic bacterium, it is a representative of universal phytopathogenic bacteria, is a multipathic spoilage bacterium that easily causes resistant bacteria and violates many plants. Tomato canker scab (scientific name: Corynebacterium michiganese pv. Michi)
ganese) was selected and the antibacterial activity against each sample was evaluated.

Antibacterial activity assay for bacteria: after lysis by heating
Semi-synthetic Wakimoto medium or King B medium 25mL kept at 55 ℃
And 2 mL of test bacteria (concentration 10 ⁹ / mL) were mixed, and this mixture was poured into a petri dish and solidified into a flat plate. An assay sample cut into a length of about 2 cm and a width of 3 mm was placed on this bacterial liquid mixed plate medium, and both ends of the assay sample were carefully embedded in the medium with tweezers, and the entire membranous sample was brought into close contact with the medium. Cover this with a black cloth, keep it at 20 to 25 ° C in an environment that shields light, and measure the degree of inhibition of bacterial growth in the medium near the test sample at specified time intervals by the size of the inhibition circle that appears around the sample. Was actually measured and evaluated in mm.

(2) Evaluation of antibacterial property by inhibition of growth of Escherichia coli Evaluation was carried out by a method similar to the above-mentioned inhibition of growth of bacterium pathogenic bacteria of tomato scab. However, as the medium, LB medium and LB agar medium were used. The composition of LB medium per 100 mL of distilled water was as follows. A medium that can be composed of 1.0 g of peptone, 0.5 g of yeast extract and 1.0 g of sodium chloride, 1.5 g of agar
The pH of the medium after sterilization was adjusted to 7.0 to 7.4. The specific culture method is as follows.

(B) E. coli was grown overnight with shaking at culturing temperature of 35 ° C. in LB medium.

(B) LB agar medium dissolved at about 60 ° C. and LB medium containing the grown Escherichia coli were mixed in equal amounts and poured into a sterilized container.

(C) After the medium was solidified, the test sample was placed on the surface of the medium.

(D) After culturing for a certain period of time, the size of the inhibition circle was observed and evaluated in mm.

(3) Dyeing amount A sample of dyed polymer material was treated with a 25 to 75% pyridine solution having a bath ratio of 1:20 to decolorize it. Colorimeter for absorbance of decolorizing solution
It was measured by Spectronic 20 (manufactured by Shimadzu Corporation), and the dyeing amount (× 10 ⁻⁵ eq / g · fiber) was determined from the calibration curve of the absorbance and the dye concentration.

In addition, the amount of dyeing of the dyed polymer material to the sample is relatively determined by the naked eye based on the following criteria.
It was evaluated on a 4-point scale.

+++: Shows a considerably high surface concentration.

++: Indicates a normal surface concentration.

+: The surface density is below normal.

-: No dyeing is observed.

(4) Whiteness Evaluation The surface concentration of the dyed polymer material sample was evaluated with a spectrophotometer (Shimadzu's own spectrophotometer, UV-3100S). Wavelength: 350-
800nm, Slit width: 2.0mm, Light source used: C, View angle 2 °
Met. It was measured with a color display system based on L, a.b. The L value (brightness) is called the degree of dye adsorption.

(5) Mechanical properties: The mechanical properties of the samples were measured, and the strength and elongation of the samples at the time of cutting were evaluated. The measurement conditions are: sample length 10 mm, width 2 mm, pulling speed 10 mm / mi
n, full scale 250 g, measured with a tensile tester (autograph, model AGS-5D) manufactured by Shimadzu Corporation.

(6) Thermal decomposition temperature: using a differential thermal scanning measuring device (DSC-10A) manufactured by Rigaku Denki Co., Ltd., with a sample weight of 2.2 mg, a DSC range of 2.5 mcal / s, and a heating rate of 10 ° C./min. The measurement was performed in a nitrogen stream of 200 mL / min. The endothermic peak temperature appearing at 200 ° C. or higher in this measurement was defined as the thermal decomposition temperature of the sample.

(7) Adsorption rate The adsorption rate was determined as follows from the concentration of the dyeing bath before and after dyeing. That is, the residual dye solution is diluted 5 times,
The absorbance at a wavelength of 505 nm was measured by Shimadzu's own spectrophotometer (MPC-31
00 / UV-3100S). Separately from this, the absorbance of a stock solution of a predetermined concentration with different concentrations was determined and a calibration curve was prepared.
The absorbance values of various dye residual solutions at 505 nm were applied to a calibration curve to obtain the respective dye concentrations, and the adsorption rate was calculated from the following formula.

Adsorption rate (%) = (Dyeing bath concentration before dyeing-Dyeing bath concentration after dyeing) / (Dyeing bath concentration before dyeing) (8) Salt shrinkage ratio When immersed in an aqueous solution and subjected to heat treatment, the molecules of the material react with neutral salts and the material shrinks in the fiber length direction. The salt reduction rate (%) was calculated using the following formula.

Salt shrinkage ratio (%) = (Li−Lf) / Li × 100 In the above formula, Li represents the material length before shrinkage, and Lf represents the material length after shrinkage. Example 1 (Evaluation of antibacterial property of gold-containing dye) The antibacterial activity of the dye itself containing various metals on the growth of tomato canker bacterium was examined. The results obtained are shown in Table 1.

It is clear from Table 1 that the gold-containing dye containing an antibacterial metal has an action of suppressing the growth of tomato canker scab, which is a pathogenic bacterium, and the antibacterial activity depends on the kind of the contained metal. However, the antibacterial activity of gold-containing dyes containing Cr is higher than that of Co. Example 2 (Effect of Pretreatment with Neutral Salt Aqueous Solution) The specific gravity was adjusted to 1.41 g / cm ³ using a Baume standard hydrometer.
A silk thread sample was dipped in an aqueous calcium nitrate solution and heated at 80 ° C. for 10 minutes to shrink the silk thread length (sometimes referred to as salt shrinkage). The salt shrinkage rate calculated from the change in sample length before and after the salt shrinkage treatment was 25%. In the same manner as in Example 1,
The salt-condensed sample was dyed with Kayakalan Black 2RL which is a metal-containing dye. The bath ratio was 1: 100, and ammonium dye as a dyeing aid was not used. The dyed amount of the dyed salt-shrink sample and the control sample (sample dyed without salt-shrink) was measured. The obtained results are shown in Table 2. (Table 2)

As is clear from Table 2, the amount of dyed salt-condensed sample was larger than that of the control sample, and more of the metal-containing dye was adsorbed on the fiber. This is because when the silk thread is dipped in an aqueous solution of a neutral salt, the length of the silk thread shrinks, the silk fibroin molecules are disturbed, and the metal-containing dye easily diffuses inside the fiber.
The dyed amount of the salt shrink sample of Sample No. 1 is 21.8 × 10 ^-5 eq / g ・ fibe
It was r. From this, when calculated according to the description of the above "(7) Adsorption rate", in preparing the antibacterial silk thread, the adsorption rate of the silk thread pretreated with the neutral salt is preferably a value of 10 or more. .

How the mechanical properties of the salt-shrinking sample of sample No. 3 (salt shrinkage ratio of 25%) in Table 2 change before and after the dyeing treatment, and when the salt-shrinking treatment or the dyeing treatment is not performed, the salt-shrinking treatment is performed. When the dyeing process was performed without treatment, the salt shrink treatment was performed, but the evaluation was made in comparison with the case where the dyeing process was not performed. Also, perform DSC measurement,
The thermal decomposition temperature of silk fibroin was measured. The results obtained are shown in Table 3. (Table 3)

In Table 3, B (cont), B + dye, B + salt,
The abbreviations of B + salt + dye and B + salt + dye are the control group which is neither salt shrinking nor dyeing processed, the control group which is dyeing processed (corresponding to the control sample of sample No. 3) and salt shrinking treatment, respectively. It refers to the salt-condensed sample of sample No. 3, which is not dyed. As the dye, a gold-containing dye Kayakalan Black 2RL was used. The numbers in parentheses in the table indicate standard deviations.

From the results shown in Table 3, the strength of the silk thread before and after dyeing does not change so much, but the elongation is slightly increased. Therefore, when the silk thread is treated with a neutral salt and then dyed, the elongation is increased. It was confirmed that the decrease in strength was small. Example 3 (Physical characteristics of neutral salt treated sample) A silk thread was dipped in a calcium nitrate aqueous solution having a specific gravity of 1.43 g / cm ³ and 80 ° C. for different times to prepare samples having different shrinkage rates of silk length, and the salt shrinkage rate. The relationship between the birefringence of silk fibers, the degree of molecular alignment, and the dyeing rate was investigated. The results obtained are shown in Table 4. In the table, the immersion time for each of sample Nos. 5, 6, 7, 8 and 9 is 10
Seconds, 30 seconds, 2 minutes, 3 minutes, and 3 minutes and 30 seconds. Sample No. 4 means a sample not subjected to any pretreatment. (Table 4)

Note: Maximum birefringence = 68 × 10 ^-3 (Δn of crystalline region) Degree of molecular arrangement = Δn / 68 × 10 ^-3 × 100 (a measure of how close to an ideal arrangement) Control group ( The degree of molecular arrangement of the silk thread (without dipping or dyeing) was about 83%. The degree of molecular arrangement is a measure of how much the non-crystalline region is inserted, as compared with the ideal state in which it is assumed that all silk threads are made of the crystalline region.

The unimmersed silk thread (Sample No. 4) had a degree of molecular arrangement of 82% and a dyeing amount of 18.5. From this, in order to efficiently adsorb the metal-containing dye to the silk thread, it is preferable to reduce the molecular arrangement degree of the silk thread to 75% or less by pretreatment with a neutral salt. Example 4 (Effect of Pretreatment with Alkaline Aqueous Solution) Sodium hydroxide aqueous solutions having different concentrations (0.4, 0.6%) were prepared.
2.5 g of silk cloth (JIS L0803-1974, conforming to the attached white cloth for dyeing fastness test; hereinafter also abbreviated as silk cloth) at 20 ° C
Soaked for 20 minutes. After the impregnation rate was set to 100%, the treated silk cloth was placed in a vinyl bag, sealed, and placed in a thermostat at 30 ° C. for 24 hours for treatment. After the reaction treatment, it was washed with water to prepare a pretreated silk cloth. The silk cloth thus prepared,
Abbreviated as N-040 and N-060. 1g of each of these silk cloths
/ L nonionic surfactant (trade name: Score Roll 40
0, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) at 75 ° C., 20
It was treated for a minute and soaped to obtain a silk cloth sample for dyeing. The bath ratio was 1: 100.

The silk cloth sample was immersed in each of the dyeing baths of 40 ° C. containing 0, 0.5, and 1% of ammonium acetate based on the weight of the silk cloth sample obtained above, immersed for 15 minutes, and then dissolved in advance. 1% dye (Kayakalan Black 2RL) was added and soaked for another 10 minutes. Then gradually increase to 90 ± 2 in 50 to 60 minutes
The temperature of the dyeing bath was raised to ℃ and dyeing was performed at that temperature for 60 minutes. Then, the dyed silk cloth was taken out, washed with water and naturally dried. After the pretreatment, the dye absorbance, the pH of the residual dyeing solution, the L value (brightness) and the dyed amount of the dyed silk cloth were determined. The results obtained are shown in Table 5.

Note: The smaller the L value, the deeper the color is dyed.

As is clear from Table 5, it was demonstrated that the pretreatment with sodium hydroxide increased the amount of dye adsorbed, that is, the antibacterial activity was strengthened. Example 5 (Effect of Pretreatment with Chitosan Aqueous Solution) A silk cloth was dipped in 10 g / L chitosan and 3 mL / L acetic acid aqueous solution,
Chitosan treatment was performed by the pad-dry-cure method (cure condition: 150 ° C., treatment for 10 minutes). Then, it was washed with water and naturally dried, and the attachment rate of chitosan was determined from the weight difference before and after the treatment.

Acid dye Orange II and gold dye Kaya
It carried out at 80 degreeC for 60 minutes using kalan Black 2RL. The dyeing concentration was calculated from the reflectance at the maximum absorption wavelength of the dye using a spectrophotometer, and the K / S value was calculated from the Kubelker-Munk equation. The obtained results are shown in Table 6.

As is clear from Table 6, it was confirmed that a large amount of dye diffused and adsorbed inside the sample by immersing the silk cloth in the chitosan aqueous solution and performing the pad-dry-cure treatment. Example 6 (antibacterial activity) The pretreated samples prepared in Examples 2-5 were used as a gold dye Kayaka.
Staining with lan Black 2RL was performed to examine the growth inhibition of tomato canker bacillus on the sample after staining. The results obtained are shown in Table 7.

As is clear from Table 7, the sample dyed after the pretreatment has a large amount of dyeing, and therefore, it has an antibacterial activity. Example 7 (Evaluation of outflow of metal from dyed product) The presence or absence of outflow of metal from a dyed product dyed with a metal-containing dye was evaluated by a dyeing fastness test with alkaline sweat. As dyes, Eriosin Brill. Cyanine G and Erio
sin Fast Blue B (even dyeing acid dye), and Irgalan
Yellow 2GL and Lanacron Navy Blue B (gold dye)
Was used to dye silk cloth by a conventional dyeing method.

The fastness to alkaline sweat is a practical evaluation value corresponding to the fastness to washing. Using a hydrotester with a 1N alkaline sweat solution, the attached silk cloth contamination was judged on a gray scale after being left at 37 ° C for 4 hours (SNV test, 1958 2
4/1961). As a result, the alkali sweat fastness of the silk cloth dyed with the Eriosin dye was grade 1, and the alkali sweat fastness of the silk cloth dyed with the Irgalan and Lanacron dyes was grade 4-5. The larger the value of the alkali sweat fastness, the less the detachment of the dye from the silk cloth when the dyed product is washed with water. That is, once the metal-containing dye is adsorbed on the silk cloth,
Since the metal ion is attached to the dye as a complex, the dyeing fastness is good, and the dye does not easily flow out from the dyed product.
Thus, there is little risk of metal spilling from the dyed product. Example 8 (Antibacterial test of dyed product) Gold-containing dye (Kayakalan Yellow GL and Kayakalan Black
The growth inhibition of Escherichia coli and tomato canker bacterium on silk cloth dyed at a concentration of 2RL) of 20% (vs. fiber weight) was examined. The results obtained are shown in Table 8.

Note: The degree of antibacterial activity was evaluated by measuring the size of the corresponding inhibition circle in mm.

From Table 8, the gold-containing dye (Kayakalan Yellow GL
And Kayakalan Black 2RL) have been found to suppress the growth of Escherichia coli and tomato canker bacilli.

Next, the copper-containing dye Kayarus Supra Rubine BL
And Kayarus Tug. Blue GL and a metal dye containing cobalt, Kayakalan Brown GL, were used to dye silk cloth. Ammonium acetate 5%, glacial acetic acid 2% by weight of silk cloth
%, The silk cloth was put into a 40 ° C. dyeing bath, and after soaking for 15 minutes, 20% of dye which had been dissolved in advance was added and treated for another 15 minutes. For dyeing, raise the dyeing bath to 90 ° C in 40 minutes, dye at the same temperature for 30 minutes, and add 1% glacial acetic acid for another 30 minutes.
I went for a minute. After dyeing, the dyeing bath was cooled to 50 ° C., the silk cloth was taken out, washed with water and air-dried. The results obtained are shown in Table 9.

Note: A and B mean inhibition circles showing antibacterial activity against tomato canker bacillus and E. coli, respectively.

As is clear from Table 9, the silk cloth dyed with the copper-containing dye and the metal dye containing cobalt inhibited the bacterial growth. Example 9 Polyester spun fiber was used for the weft yarn, and the following 9 types of fibers having different chemical compositions were used for the warp yarn. The multi-woven mixed woven fabric (JIS L0803-1974, attached white fabric for dyeing fastness test (mixed woven fabric) No. A)) in the same manner as in Example 1
It was stained with ayakalan Black 2RL. The dyed amount on each fiber was visually evaluated as described in “(3) Adsorption amount” above, and the L value was measured. The results obtained are shown in Table 10.

From Table 10, in view of the results of visual evaluation, it can be judged that fibers having an L value of about 48 or less are the materials usable in the present invention. Example 10 (Mordant effect of antibacterial metal) A silk cloth was dyed with vegetation using an onion skin and an extract from Shibuki of the peach family.

(1) Onion (skin) dyeing with vegetation A yellow-brown pigment contained in the brown outer skin of the onion was used as a dye for vegetation. In order to extract the pigment, 30 times the amount of water of the skin was added to the surface of the onion, which was 100% of the weight of the silk cloth, and the operation of boiling for 60 minutes was repeated twice. Hot water was added to the onion extract obtained as described above to adjust the volume to 50 times the weight of the dyed product, and then 1 to 2% of acetic acid was added to prepare a dyebath. Into this dyebath, put a silk cloth separately soaked in hot water and well moistened, and raise the temperature to 80 ~.
After dyeing at 90 ° C. for 30 minutes, it was washed with water.

Then, 50 times the amount of the dyed bun solution (water)
In 1 L, 2 g of crystalline light bun, 0.2 g of crystalline sodium carbonate) are made, and the dyed product obtained as described above is put in this bright bun solution,
It was mordanted at room temperature to 30 ° C for 15 minutes and washed with water. In addition,
The mixture was washed with 30 to 50 times the amount of sodium bicarbonate solution (1 g of sodium bicarbonate in 1 L of water) and washed with water.

Copper mordanting was carried out using a copper sulfate solution instead of the light bun solution. That is, a 50-fold amount of a copper sulfate solution (0.5 g of copper sulfate in 1 L of water) of the dyed product was prepared, and the dyed product was put in this solution, mordanted at room temperature to 30 ° C for 15 minutes, and washed with water. Furthermore, a baking soda solution of 30 to 50 times the amount of the dyed product (1 g of baking soda in 1 L of water)
I went inside and washed it with water.

(2) Shibuki Extract (Yamamomoaceae) To Shibuki extract (100% of the weight of the dyed product) was added 20 times the amount of water, dissolved by boiling, and filtered. Hot water was added to the solution of Shibuki extract to make the volume 50 times the amount of the dyeing solution, and then 1 to 2% of acetic acid was added to prepare a dyeing bath. Into this dyebath, separately put the dyed product in a warm water soaked well, raise the temperature, and heat at 80-90 ° C for 30
After dyeing for a minute, it was washed with water.

A stannous chloride solution (2 g of stannous chloride in 1 L of water) of 50 times the amount of the dyed product was then prepared, and the dyed product obtained as described above was placed in this solution at room temperature to 30 ° C. It was mordanted at ℃ for 15 minutes and washed with water. Further, the dyed product was washed with a 30 to 50-fold amount of sodium bicarbonate solution (1 g of sodium bicarbonate in 1 L of water) and washed with water.

Copper mordanting was carried out using a copper sulfate solution instead of the stannous chloride solution. The extract was dissolved and dyed in the same manner as in the tin mordant. That is, the dyed product
Make 50 times the amount of copper sulfate solution (0.5 g of copper sulfate in 1 L of water), put the dyed product in this solution, and mordante at room temperature to 30 ° C for 15 minutes,
Washed with water. In addition, a baking soda solution of 30 to 50 times the amount of the dyed product (1 L of water
Medium, baking soda 1g) and washed with water. The above dyeing and mordant steps were repeated twice.

As described above, the silk cloth dyed with the onion and the Shibuki extract was used to evaluate the growth inhibition of the tomato canker bacterium. The results obtained are shown in Table 11.

Note: Numerical blocking circles marked with * mean that the boundary is unclear, and numerical blocking circles without * mean that the boundary is clear. For example, in the case of catechin treatment area, the boundary of the 5 mm blocking circle is clear, but
The stop circle of means that the boundary is unclear.

From Table 11, it was revealed that the silk cloth dyed with a plant-derived extract inhibits the growth of tomato canker bacterium. Example 11 (Direct dye) A copper azo dye (Kayarus Supra Rubine BL) and a copper phthalocyanine dye (Kayarus Tug. Blue GL) were used to dye a silk cloth. Ammonium acetate 5 relative to the weight of silk cloth
%, 2% of glacial acetic acid, add silk cloth to 40 ° C dyeing bath, 1
After soaking for 5 minutes, 20% dye which had been dissolved in advance was added and the treatment was continued for another 15 minutes. Staining is performed by raising the temperature to 90 ° C for 40 minutes, and then for 30 minutes at the same temperature, and then adding 1% glacial acetic acid for 3 more times.
I went for 0 minutes. After the completion of dyeing, the dyeing bath was cooled to 50 ° C., the silk cloth was taken out, washed with water and naturally dried. The results obtained are shown in Table 12.

Note: A and B are inhibition circles (m) showing antibacterial activity against tomato canker bacillus and Escherichia coli, respectively.
means m).

As is clear from Table 12, the copper azo dye,
Silk cloth dyed with copper phthalocyanine dye inhibited the growth of tomato canker bacterium, although weak. Example 12 Silk fibroin fibers were completely dissolved by immersing the silk fibroin fibers in an aqueous solution of 8.5 M lithium bromide and heating at 60 ° C. for 30 minutes. Place this in a cellulose dialysis membrane and
It was replaced with tap water at ℃ for 4 days to prepare a 2% silk fibroin aqueous solution. This silk fibroin aqueous solution was spread on a polyethylene film and blown and dried at room temperature to prepare a transparent and tough silk fibroin film. The silk fibroin film thus produced was treated with a 50% aqueous methanol solution at 25 ° C. for 30 minutes to obtain a water-insoluble silk fibroin film. This water-insoluble silk fibroin membrane was immersed in a 0.2% aqueous sodium hydroxide solution at 20 ° C. for 5 minutes, and was sufficiently dried in a room temperature environment.
This silk fibroin film was then used for Ka used in Example 4.
In addition to yakalan Black 2RL, Kayakalan Yellow GL and
Dyeing with 3 kinds of Kayalax Yellow G gold dye,
It was thoroughly dried under the standard conditions of 25 ° C and 65% RH. In this way, the material obtained by chemically binding the antibacterial metal to silk fibroin was examined for the growth inhibition of tomato canker scab. The obtained results are shown in Table 13.

Note: A and B are the cases of using the silk fibroin film before and after the sodium hydroxide treatment, respectively, and the size of the inhibition circle is shown in mm.

As is clear from Table 13, as in the case of the silk cloth used in Example 4, the silk fibroin film was also pretreated with an aqueous sodium hydroxide solution and then dyed with a gold-containing dye to give a tomato. The growth inhibition of canker bacterium was improved.

Many of the dyes or mordants containing a metal used in the present invention contain chromium. When discharging chrome-containing substances into public sewers, the maximum amount of chrome is
The effluent standard stipulates that it should be kept below 2 mg / L.
Furthermore, the legal standard for tap water is 0 for hexavalent chrome.
It is less than 05mg / L. Therefore, when hexavalent chromium is contained, it is necessary to treat the wastewater by the following method. (1) Add hexavalent chromium such as potassium dichromate to reducing agent such as sodium sulfite or ferrous sulfate to make trivalent chromium with less toxicity, (2) Adsorb by activated carbon or zeolite and solidify It is desirable to dispose of hexavalent chromium by wastewater treatment, by separately or in combination with (3) not performing wastewater treatment using microorganisms.

[0082]

EFFECTS OF THE INVENTION According to the present invention, (1) a polymeric material that has been pretreated by dipping in a neutral salt aqueous solution, an alkaline aqueous solution or a chitosan solution is dyed with a dye containing an antibacterial metal. Or (2) dyeing the pretreated polymer material with a dye containing no antibacterial metal, and applying an antibacterial metal mordant to the dyed product to obtain a dyed product Therefore, the obtained dyed product has a vivid color tone and is economically and effectively imparted with an antibacterial activity having a function of suppressing an increase in pathogenic bacteria.

According to the present invention, since a metal having antibacterial activity is contained in the dye molecule, it is possible to dye the material with a color according to the purpose by selecting a dye, and it is highly durable. It is possible to provide a dyed product having antibacterial properties and a method for producing the same.

The antibacterial metal in the metal-containing dye used in the present invention is coordinated with the dye, and since the metal-containing dye is adsorbed and fixed on the polymer material, the metal does not flow out. Therefore, it is an antibacterial polymer material that can be safely used in both the clothing and non-clothing fields.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI D06P 5/22 D06P 5/22 (72) Inventor Masuhiro Tsukada 4-25-401-403 (72) Invention, Matsushiro Tsukuba, Ibaraki Prefecture Kozo Yasuda 591-7 Nakabeppu, Tsukuba, Ibaraki Prefecture (56) Reference JP-A-8-13361 (JP, A) JP-A-1-139882 (JP, A) JP-A-9-48925 (JP, A) JP 8-27675 (JP, A) JP 2001-164479 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D06P 5/00 105 D06P 1/36 D06P 1 / 673 D06P 5/22 A01N 59/16

Claims (7)

(57) [Claims] 1. Calcium chloride, potassium chloride, potassium nitrate
Pretreated by dipping with an aqueous solution of a compound selected from lucium, lithium bromide , sodium hydroxide, potassium hydroxide, potassium carbonate, potassium nitrate and sodium nitrate, or an aqueous chitosan solution, and dyed with a dye containing an antibacterial metal. An antibacterial dyeing product made of a polymer material which is a natural material selected from silk and wool, a cellulose fiber selected from rayon and acetate, or a synthetic fiber selected from acrylic, vinylon and nylon. 2. Calcium chloride, potassium chloride, potassium nitrate
Pretreated by dipping with an aqueous solution of a compound selected from lucium, lithium bromide , sodium hydroxide, potassium hydroxide, potassium carbonate, potassium nitrate and sodium nitrate, or an aqueous chitosan solution, and dyed with a dye containing no antibacterial metal. Further, an antibacterial dyeing product made of a polymeric material, which is a cellulose fiber selected from rayon and acetate or a synthetic fiber selected from acrylic, vinylon and nylon, treated with an antibacterial metal mordant. 3. A natural material selected from silk and wool,
Cellulosic fibers selected from broth and acetate,
Or selected from acrylic, vinylon and nylon
Synthetic fiber polymer material is used for calcium chloride and calcium chloride.
Lithium, calcium nitrate, lithium bromide, sodium hydroxide
Um, potassium hydroxide, potassium carbonate, potassium nitrate
And an aqueous solution of a compound selected from sodium nitrate, and
Is pre-treated by dipping with an aqueous chitosan solution and then
Dyeing with a dye containing a fungal metal to obtain a dyed product
A method for producing a characteristic antibacterial dyed product . 4. Selected from rayon and acetate
Cellulose fiber, or acrylic, vinylon and nylon
The polymer material, which is a synthetic fiber selected from
Lucium, potassium chloride, calcium nitrate, lithium bromide
Beam, sodium hydroxide, potassium hydroxide, potassium carbonate, selected from potassium nitrate and sodium nitrate reduction
Pretreatment by dipping process with compound aqueous solution or chitosan aqueous solution, and the pretreated polymer material is treated with antibacterial metal.
Dyed with a dye that does not contain, then the obtained dyed product is antibacterial
A method for producing an antibacterial dyed product, which comprises producing a dyed product by reacting an organic metal mordant . 5. The calcium chloride, potassium chloride, glass
Compound selected from calcium acid salt and lithium bromide
The concentration of the aqueous solution is 1.35~1.50g / cm ^3, diisocyanato hydroxide
Lithium, potassium hydroxide, potassium carbonate, potassium nitrate
And the concentration of an aqueous solution of a compound selected from sodium nitrate
The degree is 0.2-0.8%, and the concentration of chitosan aqueous solution is 5-20g
/ L, The method for producing an antibacterial dyed product according to claim 3 or 4, wherein 6. The natural material is silk, and the calcium chloride is used.
Sium, potassium chloride, calcium nitrate, and lithium bromide
Pretreatment process with a solution of a compound selected from thium
Reduce the molecular orientation of the silk to 75% or less,
Characterized by being performed so that the arrival rate is 10% or more
A method for producing an antibacterial dyeing product according to claim 3 or 5 . 7. The natural material is a silk fibroin film.
The method for producing an antibacterial dyed product according to claim 3 or 5, wherein