TWI592542B - Methods for dyeing microbial cellulose - Google Patents

Description

Biocellulose dyeing processing method

The present invention relates to a processing technique for biocellulose, and more particularly to a method for dyeing biocellulose.

In 1886, AJ Brown discovered that microorganisms can efficiently synthesize cellulose. Among them, Acetobacter xylinum in Acetyls is the most capable of synthesizing cellulose, and has the most large-scale production capacity. Bacterial cellulose has many unique properties, such as high mechanical strength, high water absorption, high crystallinity, and a cellulose network structure. It is a new type of biomaterial with a wide range of commercial uses. In order to expand the application of bio-cellulose, such as: medicine, beauty care, food, optical materials, etc., dyeing processing is the most direct way to produce different colors of bio-cellulose according to different fields and needs to increase bio-fiber Industrial use.

However, at present, biocellulose is rarely studied in the field of dyeing processing, and the current dyeing processing method is mainly carried out by physical blending. The color dispersion of this method is not good and the energy consumption is high, which is not conducive to large-scale industrial production.

Therefore, it is necessary to seek a dyeing processing method of biocellulose which can solve or ameliorate the above problems.

Some embodiments of the present invention provide a method of dyeing a biocellulose, comprising: preparing biocellulose; pretreating biocellulose; preparing dyeing Liquid, and dispersing the dye in the dyeing solution in a first ultrasonic oscillating step; mixing the oscillating and dispersed dyeing solution with biocellulose, and dyeing the biocellulose in a second ultrasonic oscillating step to form a dyed biofiber Coloring; fixing the dyed biocellulose; and washing the dyed biocellulose.

According to some embodiments of the present disclosure, the step of preparing biocellulose comprises fermenting Acetobacter xylinum to form biocellulose.

According to some embodiments of the present disclosure, the step of pretreating the biocellulose comprises sequentially washing the biocellulose with the first alkaline solution and the first acidic solution, respectively, followed by washing the biocellulose with pure water until the biocellulose is present neutral.

According to some embodiments of the present disclosure, the step of preparing a dyeing solution comprises: dissolving a dye in a solvent to form a first solution, wherein the dye is a polar dye, and the solvent is a polar solvent; mixing the surfactant with pure water to form a second solution And mixing the first solution with the second solution to obtain a staining solution.

According to some embodiments of the present disclosure, the oscillation frequency of the first ultrasonic oscillation step is between 10,000 and 100,000 Hz, and the oscillation time is 5 minutes; the oscillation frequency of the second ultrasonic oscillation step is between 10,000 and 100,000 Hz, and The shock time is 10-30 minutes.

According to some embodiments of the present disclosure, the step of fixing the dyed biocellulose comprises sequentially fixing the dyed biocellulose with a second alkaline solution and a second acidic solution, respectively.

According to some embodiments of the present disclosure, the step of washing the dyed biocellulose comprises washing the dyed biocellulose with pure water until the dyed biocellulose is neutral.

100‧‧‧ method

101, 102, 103, 104, 105, 106, 107‧ ‧ steps

1 is a flow chart showing a method of dyeing a bio-cellulose according to some embodiments of the present invention.

Figure 2 shows the results of the fixation test of the dyed biocellulose obtained in accordance with some embodiments of the present invention.

Hereinafter, a dyeing processing method of biocellulose according to an embodiment of the present invention will be described. However, it will be readily understood that the embodiments of the present invention are susceptible to many specific embodiments of the invention and can The specific embodiments disclosed are merely illustrative of the invention, and are not intended to limit the scope of the invention.

Referring to Figure 1, there is shown a flow chart of a method 100 of dyeing processing of biocellulose in accordance with some embodiments of the present invention. In step 101, biocellulose is prepared. In some embodiments, Acetobacter xylinum, Acetobacter xylinum is provided to produce biocellulose after fermentation. In some embodiments, the synthetic biocellulose is made into a biocellulose membrane. In some embodiments of the present disclosure, the synthetic biocellulose is made into a biocellulose membrane. For a detailed method for synthesizing biocellulose from fungi and making biocellulose membranes, refer to "Paper Science and Technology", Vol. 29, No. 1, 2010 (Cui Siying), "Comparison of Bacterial Cellulose Properties Prepared by Different Culture Methods" Not to be described in detail here.

In step 102, the biocellulose is pretreated. First, the bio-cellulose is sequentially washed with the first alkaline solution and the first acidic solution, and then the bio-cellulose is washed with pure water (RO water) until the bio-cellulose is neutral (the actual pH is between 6 and 7). ). In some embodiments, the pH of the first alkaline solution is between about 8 and 10, The temperature is about 25 ° C; the pH of the first acidic solution is between about 3-5 and the temperature is about 25 ° C. In some embodiments, the first alkaline solution can be an aqueous solution of sodium hydroxide, and the first acidic solution can be an aqueous solution of citric acid.

In step 103, a staining solution is prepared. First, a dye is dissolved in a solvent to form a first solution, and a surfactant is mixed with pure water to form a second solution, and then the first solution is mixed with the second solution to prepare a dyeing solution. In some embodiments, the dye comprises from about 0.01% to about 2% by volume of the first solution, and the volume ratio of surfactant to dye is from about 1:1 to 1:20, and the volume ratio of surfactant to pure water. It is about 1:10-1:25.

In some embodiments, the dye may be an edible natural or artificial color, the dye may also be a vegetable pigment, an animal pigment, a microbial pigment or a vitamin, and the dye may be a reactive dye. In some embodiments, the dye is a polar dye and the solvent is a polar solvent (eg, methanol, ethanol, propanol, isopropanol, formic acid, acetic acid, or a combination of the foregoing). In some other embodiments, the solvent can be a non-polar solvent (ethyl acetate, ethyl butyrate, benzene, toluene, or a combination of the foregoing) or other suitable solvent to match the ingredients of the dye.

In some embodiments, a dye having a smaller molecular weight than a conventional dye (the molecular weight of the polymer dye exceeds 10,000 g/mole) is selected to have a molecular weight of between about 200 and 500 g/mole.

In some embodiments, the surfactant may comprise an anionic surfactant (eg, a fatty acid salt, an alkyl benzene sulfonate, an alkyl sulfate, an alkyl phosphate, or a combination thereof), a cationic surfactant ( For example, a first fatty amine salt, a fourth ammonium salt, a trialkyl benzalkonium salt, an alkyl pyridinium salt or a combination thereof, a nonionic surfactant (for example, a polyoxyethylene alkyl ether, a polyoxygen) Ethylene alkyl phenyl ether, a polyoxyethylene fatty acid ester or a combination thereof, a two-ionic surfactant (for example, N,N-dialkylamino olefin carboxylate, N,N,N-trialkyl-N-sulfene) Ammonium salt or a combination of the foregoing).

In accordance with an embodiment of the present disclosure, in step 104, the dye in the dyeing liquor prepared in step 103 is dispersed using a first ultrasonic oscillating step. In some embodiments, the first ultrasonic oscillating step has an oscillating frequency between about 10,000 and 100,000 Hz and an oscillating time of about five minutes.

In accordance with an embodiment of the present disclosure, in step 105, the biocellulose is dyed using a second ultrasonic oscillating step. First, the smear-dispersed staining liquid in step 104 is mixed with the pre-treated biocellulose in step 102, and subjected to shock dyeing in a second ultrasonic oscillating step to prepare dyed biocellulose. In some embodiments, the volume percentage of dye in the dyed biocellulose is between 0.5 and 2%. In some embodiments, the second ultrasonic oscillating step has an oscillating frequency between 10,000 and 100,000 Hz and an oscillating time of approximately 10 to 30 minutes.

According to the embodiment of the present disclosure, the dye in the dyeing liquid is oscillated and dispersed by the ultrasonic oscillating device, and the bio-cellulose is dyed by ultrasonic vibration, which can greatly accelerate the introduction of the dye into the bio-cellulose and shorten the bio-cellulose. The dyeing time, and the dye used in the examples of the present invention has a smaller molecular weight than the dye used conventionally, and the speed of dyeing with the biocellulose bond is greatly increased, so that compared with the conventional biofiber The dyeing method achieved by physical blending can reduce the dyeing time by more than half in the embodiment of the present invention.

Furthermore, the dye in the dyeing solution is oscillated by the ultrasonic oscillating device, and the bio-cellulose is dyed by ultrasonic vibration, which can improve the dispersibility of the dye in the dyeing solution and increase the chance of bonding the dye to the bio-cellulose. And then descend The proportion of dye required for low addition.

The dyed biocellulose is represented by the following Chemical Formula 1, wherein (C ₆ H ₁₀ O ₅ )n is biocellulose and D is a polar dye. In some embodiments, during the dyeing process, due to the resonance action of the dye groups, as shown in the following chemical formulas 2.1-2.4, the polar dye D moiety is positively charged and partially negatively charged, thereby passing the intermolecular attraction force and the biofiber. The hydroxyl group in the (C ₆ H ₁₀ O ₅ ) _n forms a hydrogen bond to achieve the purpose of dyeing. In some embodiments, the polar dye D is a reactive dye, and the reactive groups in the reactive dye react with the hydroxyl groups in the biocellulose (C ₆ H ₁₀ O ₅ ) _n to form a covalent bond during the dyeing process. Become a "dye-fiber" compound.

[Chemical Formula 2.3]

Hydrogen bonding or covalent bonding through the polar dye to replace the water bound to the biocellulose before the dyeing (the moisture contained in the biocellulose), ie, contained in the polar dye and biocellulose. The water is subjected to a displacement reaction. According to the embodiment of the present disclosure, the reaction rate of the displacement reaction can be increased by using ultrasonic oscillation, and can be performed under normal temperature and normal pressure, thereby reducing the manufacturing cost of the dyed biocellulose, and the hydrogen of the polar dye and the biocellulose. A bond or covalent bond can increase the fixation rate of the dyed biocellulose.

Next, in step 106, the dyed biocellulose is fixed. First, the dyed biocellulose is subjected to alkali washing and solidification, and the dyed biocellulose is soaked in a second alkaline solution. In some embodiments, the pH of the second alkaline solution is between about 8-10, the temperature is about 25-80 ° C, and the soaking time of the dyed biocellulose in the second alkaline solution is about 30- 60 minutes. Next, the dyed biocellulose is pickled and fixed, and the dyed biocellulose is soaked in a second acidic solution. In some embodiments, the pH of the second acidic solution is between about 3-5, the temperature is about 25 °C, and the soaking time of the dyed biocellulose in the second acidic solution is about 24-48 hours. In some embodiments, the second alkaline solution can comprise an aqueous solution of sodium hydroxide and the second acidic solution can comprise an aqueous solution of citric acid.

Next, in step 107, the dyed biocellulose is washed. After the fixing treatment is completed, the dyed biocellulose is washed with pure water (RO water) until the dyed biocellulose is neutral (actual pH between 6 and 7) to remove residual acidic/alkaline solution. , solvents for dissolving dyes, surfactants, etc.

Referring to Figure 2, there is shown the results of the fixation test of dyed biocellulose prepared in accordance with some embodiments of the present invention. In one embodiment, after the dyeing process 100 of biocellulose is completed, the dyed biocellulose is subjected to an alkali washing treatment, and the fixing rate of the dyed biocellulose can be maintained at 95% or more within 30 minutes. In another embodiment, after the dyeing process 100 of biocellulose is completed, the dyed biocellulose is subjected to a water washing treatment, although the fixing rate of the dyed biocellulose is slightly lower than that of the alkaline washing, but The fixation rate of the dyed biocellulose can still be maintained above 95% within 30 minutes. In another embodiment, after the dyeing process 100 of biocellulose is completed, the serum is then added to the dyed biocellulose, although the solidification rate of the dyed biocellulose is compared to that of alkaline or water wash. It is slightly lowered, but within 30 minutes, the fixing rate of the biocellulose dyed with the essence can be maintained at 95% or more. In this embodiment, the essence is mainly an essence of a skin care product, which contains an active ingredient such as moisturizing, whitening, and anti-wrinkle.

According to some embodiments of the present invention, the dyeing processing method of biocellulose uses a ultrasonic oscillating device to oscillate the dye in the dyeing solution, and uses ultrasonic oscillating in the dyeing step of the biocellulose, which can greatly improve the efficiency of the dyeing process. Shortening the dyeing time can also improve the dispersibility of the dye in the dyeing solution, increase the chance of dye-biocellulose bonding, reduce the proportion of dyeing solution required, and use a dye with a smaller molecular weight. The rate at which cellulose bonds are dyed is also greatly increased.

In addition, since the polar dye and the biocellulose are hydrogen-bonded or covalently bonded during the dyeing process of the biocellulose, the reaction rate of the reaction can be increased by using ultrasonic vibration, and can be carried out at normal temperature and pressure. The manufacturing cost of the dyeing process of biocellulose can be reduced, and the hydrogen bonding or covalent bonding of the polar dye to the biocellulose can improve the fixing rate of the dyed biocellulose.

The dyeing processing method of the biocellulose of the embodiment of the invention can be applied to the fields of medicine, cosmetic maintenance (for example, mask or artificial dressing), food, papermaking and the like.

While the invention has been described above in terms of the preferred embodiments thereof, which are not intended to limit the invention, the invention may be modified and combined with the various embodiments described above without departing from the spirit and scope of the invention. example.

100‧‧‧ method

101, 102, 103, 104, 105, 106, 107‧ ‧ steps

Claims (12)

A method for dyeing biological cellulose, comprising: preparing a biocellulose; pretreating the biocellulose; preparing a staining solution, and dispersing a dye in the dyeing solution by a first ultrasonic oscillating step; Dispersing the dyed liquid after mixing with the biocellulose, and dyeing the biocellulose by a second ultrasonic oscillating step to form a dyed biocellulose; fixing the dyed biocellulose; And washing the dyed biocellulose. The method for dyeing bio-cellulose according to claim 1, wherein the step of preparing the bio-cellulose comprises fermenting the bio-cellulose using Acetobacter xylinum. The method for dyeing bio-cellulose according to claim 1, wherein the step of pretreating the bio-cellulose comprises sequentially washing the bio-fiber with a first alkaline solution and a first acidic solution, respectively. The biocellulose is then washed with pure water until the biocellulose is neutral. The method for dyeing bio-cellulose according to claim 1, wherein the step of preparing the dyeing solution comprises: dissolving the dye in a solvent to form a first solution, wherein the dye is a polar dye, and the dye The solvent is a polar solvent; Mixing a surfactant with pure water to form a second solution; and mixing the first solution with the second solution to obtain the staining solution. The method for dyeing bio-cellulose according to claim 4, wherein the dye accounts for 0.01-2% by volume of the first solution, and the volume ratio of the surfactant to the dye is 1: 1-1:20, the volume ratio of the surfactant to pure water is 1:10-1:25. The method for dyeing bio-cellulose according to claim 1, wherein the step of fixing the dyed biocellulose comprises sequentially applying a second alkaline solution and a second acidic solution, respectively. The stained biocellulose is fixed. The method of dyeing bio-cellulose according to claim 1, wherein the step of washing the dyed biocellulose comprises washing the dyed biocellulose with pure water until the dyed biocellulose is neutral. The method for dyeing bio-cellulose according to claim 1, wherein the dye has a volume percentage in the dyed biocellulose of 0.5-2%, and the dye has a molecular weight of 200-500 g/ Between mole. The method for dyeing bio-cellulose according to claim 1, wherein the dye comprises an edible natural or artificial color. The method for dyeing bio-cellulose according to claim 1, wherein the dye comprises a reactive dye. The method for dyeing bio-cellulose according to claim 1, wherein the first ultrasonic oscillating step has an oscillation frequency of Between 10000-100000 Hz, and the oscillation time is 5 minutes. The method for dyeing bio-cellulose according to claim 1, wherein the second ultrasonic oscillating step has an oscillating frequency of between 10,000 and 100,000 Hz and an oscillating time of 10 to 30 minutes.