CN113832562B - Large biological viscose fiber containing lily active ingredient - Google Patents
Large biological viscose fiber containing lily active ingredient Download PDFInfo
- Publication number
- CN113832562B CN113832562B CN202111343162.1A CN202111343162A CN113832562B CN 113832562 B CN113832562 B CN 113832562B CN 202111343162 A CN202111343162 A CN 202111343162A CN 113832562 B CN113832562 B CN 113832562B
- Authority
- CN
- China
- Prior art keywords
- lily
- chitosan
- dry powder
- coated
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Artificial Filaments (AREA)
Abstract
A large biological viscose fiber containing lily active ingredient comprises the preparation of chitosan-coated lily dry powder microsphere, the preparation of chitosan-coated lily dry powder microsphere dispersion liquid, the preparation of blending spinning solution, spinning and post-treatment. The dry and wet breaking strength of the original viscose fiber is 2.72cN/dtex and 1.89cN/dtex, the breaking elongation is 24.4%, and the dry and wet breaking strength of the viscose fiber containing the lily active ingredient prepared by the invention is 2.65-2.93 cN/dtex and 1.71-1.86 cN/dtex, and the breaking elongation is 22.9-24.8%; the antibacterial rates of staphylococcus aureus, escherichia coli and candida albicans are 93.5-96.6%, 92.8-94.7% and 91.8-92.3%, respectively, and the corresponding antibacterial rates after 30 times of washing are 90.8-94.3%, 88.4-91.5% and 87.9-89.6%, respectively.
Description
Technical Field
The invention relates to a large biological viscose fiber containing lily active ingredients, and belongs to the technical field of viscose fibers.
Background
The viscose fiber has the characteristics of good hygroscopicity, good air permeability, easy dyeing, soft and glossy hand feeling, super-strong antistatic performance, good wearing comfort and the like, is particularly suitable for being used as a close-fitting clothing fabric, and along with the improvement of technological progress and living standard, the viscose fiber textile is being converted from practical type to functional type, and the viscose fiber with antibacterial property, skin care property or other medical care functions is increasingly favored by the market.
The lily contains various bioactive substances such as natural plant proteins, polysaccharide bodies, steroid saponins, phenolic compounds, flavonoid compounds, alkaloids and the like, and has very excellent antibacterial function. In the aspect of nervous system, the pillow has the functions of calming and tranquillizing, helping sleep, resisting depression and relieving psychological stress; in the aspect of skin care, the lily bioactive substances have the effects of conditioning greasy skin, eliminating body odor, moisturizing and increasing skin elasticity, conditioning skin metabolism, softening and smoothing skin and repairing skin tissues. Thus, the incorporation of lily bioactive substances into viscose fibers will develop a fiber textile with excellent antibacterial skin care functions.
The viscose fiber introduces plant active substances, has the problem of easy loss and difficult lasting antibacterial effect, chinese patent CN103741245A discloses a viscose fiber with ginkgo leaf antibacterial function and a preparation method thereof, wherein an aqueous solution of natural ginkgo leaf extract powder is added into viscose spinning stock solution, and the viscose fiber with ginkgo leaf antibacterial function is formed by wet spinning and spinning technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a large biological viscose fiber containing lily active ingredients, which realizes the following aims: the viscose fiber containing chitosan coated lily active ingredient particles is prepared, the mechanical properties of the fiber are not affected by the doping of the particles, the durable antibacterial and skin care functions are realized, the lily active ingredient is chemically bonded into the molecular structure of the viscose fiber after being coated by the chitosan, and the loss speed of the chitosan and the lily active ingredient in the fiber washing process is slowed down.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a large biological viscose fiber containing lily active ingredient comprises the preparation of chitosan-coated lily dry powder microsphere, the preparation of chitosan-coated lily dry powder microsphere dispersion liquid, the preparation of blending spinning solution, spinning and post-treatment.
The following is a further improvement of the above technical scheme:
step (1) preparation of chitosan coated lily dry powder microspheres
1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the total mass of 0.5-0.8 times of the fresh lily, putting the fresh lily into a high-speed beating machine, beating the fresh lily into slurry at 10000-20000 revolutions per minute, putting the obtained slurry into a vacuum microwave dryer, drying the slurry to obtain dry solids with the moisture content of 0.5-1.3%, and dry-grinding the dry solids in a high-speed ball mill under 20000-35000 revolutions per minute to obtain lily dry powder with the particle size of 0.1-0.5 microns.
The specific conditions of the drying are as follows: the drying temperature is 40-60 ℃, the thickness of the slurry is 0.5-1.5 cm, the drying time is 60-80 minutes, and the pressure is-0.04 to-0.09 MPa.
2) Adding a certain amount of chitosan into an acetic acid solution with the weight percent of 1, heating to 50-70 ℃, stirring to fully dissolve the chitosan, dripping a sodium hydroxide aqueous solution to adjust the pH value to be 4-5, adding dried lily powder with the mass of 0.5-0.7 times of the chitosan, stirring for 40-80 minutes at the stirring rate of 3000-4000 rpm to obtain a uniform and stable suspension, dripping a sodium pyrophosphate aqueous solution into the suspension at the stirring rate of 10 ml/min, continuously stirring for 20-40 minutes at the stirring rate of 3000-4000 rpm to obtain a solution of chitosan-coated dried lily powder microsphere, reducing the stirring rate to 1000-2000 rpm, dripping a sodium hydroxide aqueous solution to adjust the pH value to be 7.5-8.5, stirring for 10-20 minutes, centrifuging the obtained solution to remove supernatant, washing the obtained solid with deionized water for three times, and freeze-drying at the temperature of minus 30-40 ℃ to obtain dried lily powder microsphere with the particle size of 0.3-0.8 micrometers;
the addition amount of the chitosan is 6-10% of the mass of the acetic acid solution with the weight percent of 1%;
the concentration of the sodium hydroxide aqueous solution is 0.1mol/L;
the concentration of the sodium pyrophosphate aqueous solution is 0.6-0.8 g/L, and the addition amount is 12-15% of the mass of the acetic acid solution with the weight percent.
Step (2) preparation of chitosan coated lily dry powder microsphere dispersion liquid
Heating to 40-60 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 6000-9000 rpm, and stirring and dispersing for 2-4 hours to obtain chitosan-coated lily dry powder microsphere dispersion;
the THI is S-S30 alkaline silica sol, the silicon dioxide content is 30wt%, and the particle size of colloidal particles is 20nm;
the concentration of the sodium hydroxide aqueous solution is 30-50 g/L;
the addition amount of the aminopropylamine dioleate quaternary ammonium salt is 0.7-1.1% of that of a sodium hydroxide aqueous solution;
the DY-ET113 hydrophilic reactive polyether modified polysiloxane is added in an amount of 0.3-0.5% of a sodium hydroxide aqueous solution;
the addition amount of the THI cubic S-S30 alkaline silica sol is 4-8% of that of a sodium hydroxide aqueous solution;
the added amount of the chitosan-coated lily dry powder microspheres is 3-7% of that of the sodium hydroxide aqueous solution.
Preparation of the blending spinning solution in the step (3)
Taking cellulose pulp as a raw material, carrying out steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and dissolving the yellowing product in a chitosan-coated lily dry powder microsphere dispersion to obtain blended spinning liquid;
the yellowing product is dissolved in a chitosan-coated lily dry powder microsphere dispersion liquid, and the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion liquid is 1:2-4;
the blend spinning solution, in which the A cellulose was 8.8wt%, the viscosity was 53s, and the maturity was 18mL (9.9% NH) 4 Cl）。
Step (4) spinning and post-treatment
Filtering and defoaming the blended spinning solution, spraying fine flow through a spray head of a spinning machine to form a filament bundle, feeding the filament bundle into a second bath by a first drafting machine, feeding the filament bundle into a third bath by a second drafting machine after the second bath, and feeding the filament bundle after the third bath into a post-treatment by a third drafting machine;
the coagulation bath used in one bath is 100-125 g/L sulfuric acid, 200-260 g/L sodium sulfate and 12-16 g/L zinc sulfate, the one bath temperature is 45-55 ℃, and the draft rate of one draft machine is 55-75%;
the coagulating bath used in the second bath is 16-24 g/L sulfuric acid, the temperature of the second bath is 75-90 ℃, and the draft rate of the second drafting machine is 35-45%;
the coagulation bath used in the three baths is sulfuric acid with the pH value of 1.5-2.5, the temperature of the three baths is 80-90 ℃, and the drafting rate of the three drafting machines is 6-12%;
the post-treatment is to desulfurize, float and oil the drawn filament bundles, wherein the desulfurizing agent used for desulfurization consists of sodium sulfide with the concentration of 3-7 g/L and sodium carbonate with the concentration of 2-5 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.2-0.4 g/L; the addition amount of the oiling agent used for oiling is 5-8 g/L.
The preferable technical scheme is as follows:
the step (1) is the preparation of the chitosan-coated lily dry powder microsphere
1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the total mass of 0.6 times, putting into a high-speed pulping machine, pulping at 15000 r/min, drying to obtain dry solid with the moisture content of 0.8, and dry-grinding in a high-speed ball mill under the condition of 30000 r/min to obtain lily dry powder with the particle size of 0.3 microns.
The drying conditions are as follows: the drying temperature is 50 ℃, the thickness of the slurry is 1.0 cm, the drying time is 70 minutes, and the pressure is-0.08 MPa.
2) Adding chitosan into acetic acid solution with the weight percentage of 1 percent, heating to 60 ℃, stirring and dissolving, dripping sodium hydroxide aqueous solution to adjust the pH value to be 4.5, adding dried lily powder with the weight of 0.6 times of the chitosan, stirring for 60 minutes at the stirring rate of 3500 revolutions per minute to obtain uniform and stable suspension, continuously stirring for 30 minutes at 3500 revolutions per minute after the dripping of sodium pyrophosphate aqueous solution is finished to obtain dried lily powder microsphere solution coated with chitosan, dripping sodium hydroxide aqueous solution after the stirring rate is reduced to 1500 revolutions per minute, adjusting the pH value to be 8.0, stirring for 15 minutes to generate flocculent precipitate, centrifuging to obtain solid, washing, and freeze-drying at the temperature of minus 35 ℃ to obtain dried lily powder microsphere coated with chitosan with the particle size of 0.5 microns;
the addition amount of the chitosan is 8% of the mass of the acetic acid solution with the weight percent of 1%;
the concentration of the sodium pyrophosphate aqueous solution is 0.7g/L, and the addition amount is 13.5% of the mass of the acetic acid solution with the weight percent.
Heating the mixture to 50 ℃ in a sodium hydroxide aqueous solution with a certain concentration in the step (2), adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan coated lily dry powder microspheres at 7500 r/min, and stirring and dispersing for 3 hours to obtain chitosan coated lily dry powder microsphere dispersion;
the concentration of the sodium hydroxide aqueous solution is 40g/L;
the addition amount of the aminopropylamine dioleate quaternary ammonium salt is 0.9% of that of the sodium hydroxide aqueous solution;
the DY-ET113 hydrophilic reactive polyether modified polysiloxane is added in an amount of 0.4% of a sodium hydroxide aqueous solution;
the addition amount of the THI cube S-S30 alkaline silica sol is 6% of that of a sodium hydroxide aqueous solution;
the added amount of the chitosan-coated lily dry powder microspheres is 5% of that of the sodium hydroxide aqueous solution.
Dissolving the yellowing product in the step (3) in a chitosan-coated lily dry powder microsphere dispersion liquid, wherein the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion liquid is 1:3;
the coagulation bath used in the step (4) is 115g/L sulfuric acid, 240g/L sodium sulfate and 14g/L zinc sulfate, the temperature of the one bath is 50 ℃, and the draft rate of the one-step draft machine is 65%;
the coagulating bath used in the second bath is sulfuric acid with the concentration of 20g/L, the temperature of the second bath is 80 ℃, and the draft rate of the second drafting machine is 40%;
the coagulation bath used in the three baths is sulfuric acid with pH=2, the temperature of the three baths is 85 ℃, and the draft rate of the three drafting machines is 8%; the desulfurizing agent used for desulfurizing consists of sodium sulfide with the concentration of 5g/L and sodium carbonate with the concentration of 3.6 g/L;
the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.3 g/L;
the addition amount of the oiling agent used for oiling is 7g/L.
Compared with the prior art, the invention has the following beneficial effects:
1. the viscose fiber containing chitosan-coated lily active ingredient particles is prepared by chemically bonding the lily active ingredient particles into a viscose fiber molecular structure after being coated by chitosan, has dual effects of resisting bacteria and protecting skin, has no influence on fiber strength, has the dry breaking strength of 2.72cN/dtex without adding the viscose fiber containing chitosan-coated lily active ingredient particles, has the wet breaking strength of 1.89cN/dtex, has the elongation at break of 24.4 percent, has the dry breaking strength of 2.65-2.93 cN/dtex with the chitosan-coated lily active ingredient particles, has the wet breaking strength of 1.71-1.86 cN/dtex, and has the elongation at break of 22.9-24.8 percent;
2. the viscose fiber containing chitosan coated lily active ingredient particles prepared by the invention has good and durable antibacterial effect, and the antibacterial rates of the viscose fiber on staphylococcus aureus, escherichia coli and candida albicans are 93.5-96.6%, 92.8-94.7%, 91.8-92.3%, and the corresponding antibacterial rates after 30 times of washing are 90.8-94.3%, 88.4-91.5% and 87.9-89.6%, respectively.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1: large biological viscose fiber containing lily active ingredient
The method comprises the following steps:
1. preparation of chitosan-coated lily dry powder microsphere
1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the total mass of 0.6 times, putting into a high-speed beating machine, beating into slurry at 15000 r/min, drying the obtained slurry in a vacuum microwave dryer to obtain dry solid with the moisture content of 0.8%, and dry-grinding in a high-speed ball mill under the condition of 30000 r/min to obtain lily dry powder with the particle size of 0.3 mu m.
The specific conditions of the drying are as follows: the drying temperature is 50 ℃, the thickness of the slurry is 1.0 cm, the drying time is 70 minutes, the pressure is-0.08 MPa,
2) Adding a certain amount of chitosan into acetic acid solution with the weight percent of 1, heating to 60 ℃, stirring to fully dissolve the chitosan, dripping sodium hydroxide aqueous solution to adjust the pH=4.5, adding dried lily powder with the mass of 0.6 times of chitosan, stirring for 60 minutes at the stirring rate of 3500 revolutions per minute to obtain uniform and stable suspension, dripping sodium pyrophosphate aqueous solution into the suspension at the stirring rate of 10 milliliters per minute, continuously stirring for 30 minutes at 3500 revolutions per minute after the dripping is finished to obtain dried lily powder microsphere solution coated with chitosan, reducing the stirring rate to 1500 revolutions per minute, dripping sodium hydroxide aqueous solution to adjust the pH=8.0, stirring for 15 minutes to generate flocculent precipitate, centrifuging the obtained solution after stopping stirring, discarding supernatant, washing the obtained solid with deionized water for three times, and freeze-drying at-35 ℃ to obtain dried lily powder microsphere coated with chitosan with the particle size of 0.5 micrometers;
the addition amount of the chitosan is 8% of the mass of the acetic acid solution with the weight percent of 1%;
the concentration of the sodium hydroxide aqueous solution is 0.1mol/L;
the concentration of the sodium pyrophosphate aqueous solution is 0.7g/L, and the addition amount is 13.5% of the mass of the acetic acid solution with the weight percent.
2. Preparation of chitosan-coated lily dry powder microsphere dispersion liquid
Heating to 50 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 7500 r/min, stirring and dispersing for 3 hours to obtain a chitosan-coated lily dry powder microsphere dispersion;
the THI is S-S30 alkaline silica sol, the silicon dioxide content is 30wt%, and the particle size of colloidal particles is 20nm;
the concentration of the sodium hydroxide aqueous solution is 40g/L;
the addition amount of the aminopropylamine dioleate quaternary ammonium salt is 0.9% of the mass of the sodium hydroxide aqueous solution;
the DY-ET113 hydrophilic reactive polyether modified polysiloxane is added in an amount of 0.4% of a sodium hydroxide aqueous solution;
the addition amount of the THI cube S-S30 alkaline silica sol is 6% of that of a sodium hydroxide aqueous solution;
the added amount of the chitosan-coated lily dry powder microspheres is 5% of that of sodium hydroxide aqueous solution;
in the step, aminopropylamine dioleate quaternary ammonium salt is taken as a dispersing agent, so that chitosan-coated lily dry powder microspheres can be promoted to be uniformly dispersed in an alkaline solution, DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol both have a large number of very reactive silicon hydroxyl groups, and can be chemically bonded with hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres, so that the number of active hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres is increased, the chitosan-coated lily dry powder microspheres have higher reactivity, and in the subsequent spinning solidification process, the large number of high-reactivity hydroxyl groups can react with hydroxyl groups in viscose fiber molecular structures to form firm chemical bonds.
3. Preparation of blend spinning solution
Taking cellulose pulp as a raw material, carrying out steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and dissolving the yellowing product in a chitosan-coated lily dry powder microsphere dispersion to obtain blended spinning liquid;
the yellowing product is dissolved in a chitosan-coated lily dry powder microsphere dispersion liquid, and the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion liquid is 1:3;
the blend spinning solution, in which the A cellulose was 8.8wt%, the viscosity was 53s, and the maturity was 18mL (9.9% NH) 4 Cl）；
4. Spinning and post-treatment
Filtering and defoaming the blended spinning solution, spraying fine flow through a spray head of a spinning machine to form a filament bundle, feeding the filament bundle into a second bath by a first drafting machine, feeding the filament bundle into a third bath by a second drafting machine after the second bath, and feeding the filament bundle after the third bath into a post-treatment by a third drafting machine;
the coagulation bath used in one bath is 115g/L sulfuric acid, 240g/L sodium sulfate and 14g/L zinc sulfate, the one bath temperature is 50 ℃, and the draft rate of one draft machine is 65%;
the coagulating bath used in the second bath is sulfuric acid with the concentration of 20g/L, the temperature of the second bath is 80 ℃, and the draft rate of the second drafting machine is 40%;
the coagulation bath used in the three baths is sulfuric acid with pH=2, the temperature of the three baths is 85 ℃, and the draft rate of the three drafting machines is 8%;
the post-treatment is to desulfurize, float and oil the drawn filament bundles, wherein the desulfurizing agent used for desulfurization consists of sodium sulfide with the concentration of 5g/L and sodium carbonate with the concentration of 3.6 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.3 g/L; the addition amount of the oiling agent used for oiling is 7g/L.
Antibacterial ability evaluation referring to GB/T20944-2007, antibacterial rates of the obtained viscose fiber against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were tested;
antibacterial effect wash resistance test: the detergent is commercial common washing powder with the mass concentration of 0.3%, the washing process is that the washing is carried out for 15 minutes, the washing is carried out twice with clear water for 5 minutes each time, and the detergent is naturally dried at room temperature.
The dry breaking strength of the fiber obtained in example 1 was 2.93cN/dtex, the wet breaking strength was 1.86cN/dtex, the elongation at break was 24.8%, the antibacterial rates against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were 96.6%, 94.7% and 92.3%, respectively, and the corresponding antibacterial rates after 30 washing were 94.3%, 91.5% and 89.6%, respectively.
Example 2: large biological viscose fiber containing lily active ingredient
The method comprises the following steps:
1. preparation of chitosan-coated lily dry powder microsphere
1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the total mass of 0.5 times, putting into a high-speed pulping machine, pulping at 10000 revolutions per minute to obtain slurry, drying the obtained slurry in a vacuum microwave dryer to obtain dry solid with the moisture content of 0.5%, and dry-grinding in a high-speed ball mill under 20000 revolutions per minute to obtain lily dry powder with the particle size of 0.1 microns.
The specific conditions of the drying are as follows: drying at 40deg.C for 60 min at a slurry thickness of 0.5 cm and a pressure of-0.04 MPa;
2) Adding a certain amount of chitosan into acetic acid solution with the weight percent of 1, heating to 50 ℃, stirring to fully dissolve the chitosan, dripping sodium hydroxide aqueous solution to adjust the pH value to be 4, adding lily dry powder with the mass of 0.5 time of chitosan, stirring for 40 minutes at the stirring rate of 3000 r/min to obtain uniform and stable suspension, dripping sodium pyrophosphate aqueous solution into the suspension at the stirring rate of 10 ml/min, continuously stirring for 20 minutes at the stirring rate of 3000 r/min to obtain a chitosan-coated lily dry powder microsphere solution, reducing the stirring rate to 1000 r/min, dripping sodium hydroxide aqueous solution to adjust the pH value to be 7.5, stirring for 10 minutes to generate flocculent precipitate, centrifuging the obtained solution, discarding supernatant, washing the obtained solid with deionized water for three times, and freeze-drying at the temperature of minus 30 ℃ to obtain chitosan-coated lily dry powder microsphere with the particle size of 0.3 microns;
the addition amount of the chitosan is 6% of the mass of the acetic acid solution with the weight percent of 1%;
the concentration of the sodium hydroxide aqueous solution is 0.1mol/L;
the concentration of the sodium pyrophosphate aqueous solution is 0.6g/L, and the addition amount is 12% of the mass of the acetic acid solution with the weight percent of 1.
2. Preparation of chitosan-coated lily dry powder microsphere dispersion liquid
Heating to 40 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI [ S ] -S30 alkaline silica sol, chitosan-coated lily dry powder microspheres into the aqueous solution at 6000 rpm, and stirring and dispersing the mixture for 2 hours to obtain chitosan-coated lily dry powder microsphere dispersion;
the THI is S-S30 alkaline silica sol, the silicon dioxide content is 30wt%, and the particle size of colloidal particles is 20nm;
the concentration of the sodium hydroxide aqueous solution is 30g/L;
the addition amount of the aminopropylamine dioleate quaternary ammonium salt is 0.7% of the mass of the sodium hydroxide aqueous solution;
the DY-ET113 hydrophilic reactive polyether modified polysiloxane is added in an amount of 0.3% of a sodium hydroxide aqueous solution;
the addition amount of the THI cubic S-S30 alkaline silica sol is 4% of that of a sodium hydroxide aqueous solution;
the added amount of the chitosan-coated lily dry powder microspheres is 3% of that of a sodium hydroxide aqueous solution;
in the step, aminopropylamine dioleate quaternary ammonium salt is taken as a dispersing agent, so that chitosan-coated lily dry powder microspheres can be promoted to be uniformly dispersed in an alkaline solution, DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol both have a large number of very reactive silicon hydroxyl groups, and can be chemically bonded with hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres, so that the number of active hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres is increased, the chitosan-coated lily dry powder microspheres have higher reactivity, and in the subsequent spinning solidification process, the large number of high-reactivity hydroxyl groups can react with hydroxyl groups in viscose fiber molecular structures to form firm chemical bonds.
3. Preparation of blend spinning solution
Taking cellulose pulp as a raw material, carrying out steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and dissolving the yellowing product in a chitosan-coated lily dry powder microsphere dispersion to obtain blended spinning liquid;
the yellowing product is dissolved in a chitosan-coated lily dry powder microsphere dispersion liquid, and the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion liquid is 1:2;
the blend spinning solution, in which the A cellulose was 8.8wt%, the viscosity was 53s, and the maturity was 18mL (9.9% NH) 4 Cl）；
4. Spinning and post-treatment
Filtering and defoaming the blended spinning solution, spraying fine flow through a spray head of a spinning machine to form a filament bundle, feeding the filament bundle into a second bath by a first drafting machine, feeding the filament bundle into a third bath by a second drafting machine after the second bath, and feeding the filament bundle after the third bath into a post-treatment by a third drafting machine;
the coagulation bath used in one bath is 100g/L sulfuric acid, 200g/L sodium sulfate and 12g/L zinc sulfate, the temperature of one bath is 45 ℃, and the draft rate of one draft machine is 55%;
the coagulating bath used in the second bath is 16g/L sulfuric acid, the temperature of the second bath is 75 ℃, and the draft rate of the second drafting machine is 35%;
the coagulation bath used in the three baths is sulfuric acid with pH=1.5, the temperature of the three baths is 80 ℃, and the drafting rate of the three drafting machines is 6%;
the post-treatment is to desulfurize, float and oil the drawn filament bundles, wherein the desulfurizing agent used for desulfurization consists of sodium sulfide with the concentration of 3g/L and sodium carbonate with the concentration of 2 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.2 g/L; the addition amount of the oiling agent used for oiling is 5g/L.
Antibacterial ability evaluation referring to GB/T20944-2007, antibacterial rates of the obtained viscose fiber against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were tested;
antibacterial effect wash resistance test: the detergent is commercial common washing powder with the mass concentration of 0.3%, the washing process is that the washing is carried out for 15 minutes, the washing is carried out twice with clear water for 5 minutes each time, and the detergent is naturally dried at room temperature.
The dry breaking strength of the fiber obtained in example 2 was 2.77cN/dtex, the wet breaking strength was 1.71cN/dtex, the elongation at break was 23.5%, the antibacterial rates against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were 94.9%, 93.6%, 91.8%, and the corresponding antibacterial rates after 30 washing were 90.8%, 90.2% and 87.9%, respectively.
Example 3: large biological viscose fiber containing lily active ingredient
The method comprises the following steps:
1. preparation of chitosan-coated lily dry powder microsphere
1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the total mass of 0.8 times of the fresh lily, putting the fresh lily into a high-speed pulping machine, pulping the fresh lily into slurry at 20000 revolutions per minute, putting the obtained slurry into a vacuum microwave dryer for drying to obtain dry solid with the water content of 1.3%, and dry-grinding the dried solid in a high-speed ball mill under the condition of 35000 revolutions per minute to obtain lily dry powder with the particle size of 0.5 microns.
The specific conditions of the drying are as follows: the drying temperature is 60 ℃, the thickness of the slurry is 1.5 cm, the drying time is 80 minutes, the pressure is-0.09 MPa,
2) Adding a certain amount of chitosan into acetic acid solution with 1wt% and heating to 70 ℃, stirring to fully dissolve the chitosan, dripping sodium hydroxide aqueous solution to adjust pH=5, adding dried lily powder with the mass of 0.7 times of chitosan, stirring for 80 minutes at the stirring rate of 4000 rpm to obtain uniform and stable suspension, dripping sodium pyrophosphate aqueous solution into the suspension at the stirring rate of 10 ml/min, continuously stirring for 40 minutes at 4000 rpm after the dripping to obtain a solution of chitosan-coated lily dry powder microsphere, reducing the stirring rate to 2000 rpm, dripping sodium hydroxide aqueous solution to adjust pH=8.5, stirring for 20 minutes, generating flocculent precipitate, centrifuging the obtained solution, removing supernatant, washing the obtained solid with deionized water for three times, and freeze-drying at-40 ℃ to obtain the chitosan-coated lily dry powder microsphere with the particle size of 0.8 micrometers;
the addition amount of the chitosan is 10% of the mass of the acetic acid solution with the weight percent of 1%;
the concentration of the sodium hydroxide aqueous solution is 0.1mol/L;
the concentration of the sodium pyrophosphate aqueous solution is 0.8g/L, and the addition amount is 15% of the mass of the acetic acid solution with the weight percent of 1.
2. Preparation of chitosan-coated lily dry powder microsphere dispersion liquid
Heating to 60 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 9000 revolutions per minute, and stirring and dispersing for 4 hours to obtain a chitosan-coated lily dry powder microsphere dispersion;
the THI is S-S30 alkaline silica sol, the silicon dioxide content is 30wt%, and the particle size of colloidal particles is 20nm;
the concentration of the sodium hydroxide aqueous solution is 50g/L;
the addition amount of the aminopropylamine dioleate quaternary ammonium salt is 1.1% of the mass of the sodium hydroxide aqueous solution;
the DY-ET113 hydrophilic reactive polyether modified polysiloxane is added in an amount of 0.5% of a sodium hydroxide aqueous solution;
the addition amount of the THI cube S-S30 alkaline silica sol is 8% of that of a sodium hydroxide aqueous solution;
the added amount of the chitosan-coated lily dry powder microspheres is 7% of that of a sodium hydroxide aqueous solution;
in the step, aminopropylamine dioleate quaternary ammonium salt is taken as a dispersing agent, so that chitosan-coated lily dry powder microspheres can be promoted to be uniformly dispersed in an alkaline solution, DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol both have a large number of very reactive silicon hydroxyl groups, and can be chemically bonded with hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres, so that the number of active hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres is increased, the chitosan-coated lily dry powder microspheres have higher reactivity, and in the subsequent spinning solidification process, the large number of high-reactivity hydroxyl groups can react with hydroxyl groups in viscose fiber molecular structures to form firm chemical bonds.
3. Preparation of blend spinning solution
Taking cellulose pulp as a raw material, carrying out steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and dissolving the yellowing product in a chitosan-coated lily dry powder microsphere dispersion to obtain blended spinning liquid;
the yellowing product is dissolved in a chitosan-coated lily dry powder microsphere dispersion liquid, and the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion liquid is 1:4;
the blend spinning solution, in which the A cellulose was 8.8wt%, the viscosity was 53s, and the maturity was 18mL (9.9% NH) 4 Cl）；
4. Spinning and post-treatment
Filtering and defoaming the blended spinning solution, spraying fine flow through a spray head of a spinning machine to form a filament bundle, feeding the filament bundle into a second bath by a first drafting machine, feeding the filament bundle into a third bath by a second drafting machine after the second bath, and feeding the filament bundle after the third bath into a post-treatment by a third drafting machine;
the coagulation bath used in one bath is 125g/L sulfuric acid, 260g/L sodium sulfate and 16g/L zinc sulfate, the one bath temperature is 55 ℃, and the draft rate of one draft machine is 75%;
the coagulating bath used in the second bath is 24g/L sulfuric acid, the temperature of the second bath is 90 ℃, and the draft rate of the second drafting machine is 45%;
the coagulation bath used in the three baths is sulfuric acid with pH=2.5, the temperature of the three baths is 90 ℃, and the drafting rate of the three drafting machines is 12%;
the post-treatment is to desulfurize, float and oil the drawn filament bundles, wherein the desulfurizing agent used for desulfurization consists of sodium sulfide with the concentration of 7g/L and sodium carbonate with the concentration of 5 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.4 g/L; the addition amount of the oiling agent used for oiling is 8g/L.
Antibacterial ability evaluation referring to GB/T20944-2007, antibacterial rates of the obtained viscose fiber against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were tested;
antibacterial effect wash resistance test: the detergent is commercial common washing powder with the mass concentration of 0.3%, the washing process is that the washing is carried out for 15 minutes, the washing is carried out twice with clear water for 5 minutes each time, and the detergent is naturally dried at room temperature.
The dry breaking strength of the fiber obtained in example 3 was 2.65cN/dtex, the wet breaking strength was 1.81cN/dtex, the elongation at break was 22.9%, the antibacterial rates against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were 93.5%, 92.8% and 92.0%, respectively, and the corresponding antibacterial rates after 30 washing were 92.7%, 88.4% and 89.3%, respectively.
Comparative example 1: the preparation process of the chitosan-coated lily dry powder microsphere dispersion liquid does not add aminopropyldioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol
1. The preparation of the chitosan-coated lily dry powder microsphere is the same as that of example 1;
2. preparation of chitosan-coated lily dry powder microsphere dispersion liquid
Heating to 50 ℃ in sodium hydroxide aqueous solution with a certain concentration, adding chitosan coated lily dry powder microspheres at 7500 r/min, stirring and dispersing for 3 hours to obtain chitosan coated lily dry powder microsphere dispersion;
the concentration of the sodium hydroxide aqueous solution is 40g/L;
the added amount of the chitosan-coated lily dry powder microspheres is 5% of that of sodium hydroxide aqueous solution;
3. the preparation of the blend dope was the same as in example 1
4. The spinning and post-treatment were the same as in example 1
Antibacterial ability evaluation referring to GB/T20944-2007, antibacterial rates of the obtained viscose fiber against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were tested;
antibacterial effect wash resistance test: the detergent is commercial common washing powder with the mass concentration of 0.3%, the washing process is that the washing is carried out for 15 minutes, the washing is carried out twice with clear water for 5 minutes each time, and the detergent is naturally dried at room temperature;
the dry breaking strength of the fiber obtained in comparative example 1 was 2.84cN/dtex, the wet breaking strength was 1.91cN/dtex, the elongation at break was 25.6%, the antibacterial rates against three bacteria of Staphylococcus aureus, escherichia coli and Candida albicans were 95.9%, 95.4% and 91.1%, respectively, and the corresponding antibacterial rates after 30 washing were 51.7%, 48.9% and 60.2%, respectively.
Comparative example 2: chitosan-coated lily dry powder microsphere without being added into viscose fiber
1. Preparation of spinning solution
Taking cellulose pulp as a raw material, carrying out steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and dissolving the yellowing product in 40g/L sodium hydroxide aqueous solution to obtain spinning solution;
the yellowing product is dissolved in 40g/L sodium hydroxide aqueous solution, and the mass ratio of the yellowing product to the 40g/L sodium hydroxide aqueous solution is 1:3;
the spinning solution, in which the A-type cellulose was 8.8wt%, the viscosity was 53s, and the maturity was 18mL (9.9% NH) 4 Cl）；
2. Spinning and post-treatment were the same as in example 1;
the fiber obtained in comparative example 2 had a dry breaking strength of 2.72cN/dtex, a wet breaking strength of 2.13cN/dtex and an elongation at break of 24.4%.
Claims (6)
1. A large biological viscose fiber containing lily active ingredients is characterized in that: the preparation method comprises the steps of preparing chitosan-coated lily dry powder microspheres, preparing chitosan-coated lily dry powder microsphere dispersion liquid, preparing blending spinning liquid, spinning and post-treating;
the preparation of the chitosan-coated lily dry powder microsphere comprises the steps of dripping 0.1mol/L sodium hydroxide aqueous solution into a chitosan-coated lily dry powder microsphere solution under the condition of 1000-2000 revolutions/minute to adjust the pH value to be 7.5-8.5, stirring for 10-20 minutes to generate flocculent precipitate in the solution, washing the solid obtained by centrifugal separation of the solution with deionized water for three times, and freeze-drying at-30 to-40 ℃ to obtain the chitosan-coated lily dry powder microsphere with the particle size of 0.3-0.8 microns;
the preparation of the chitosan-coated lily dry powder microsphere solution comprises the steps of adding chitosan into 1wt% acetic acid solution, heating to 50-70 ℃, dropwise adding sodium hydroxide aqueous solution after the chitosan is fully dissolved to adjust pH=4-5, adding lily dry powder with the mass 0.5-0.7 times of that of the chitosan, stirring for 40-80 minutes at a speed of 3000-4000 rpm to obtain suspension, dropwise adding sodium pyrophosphate aqueous solution into the suspension at a speed of 10 ml/min, and continuously stirring for 20-40 minutes at a speed of 3000-4000 rpm after the dropwise adding to obtain the chitosan-coated lily dry powder microsphere solution;
the preparation of the chitosan-coated lily dry powder microsphere dispersion liquid comprises the steps of heating 30-50 g/L of sodium hydroxide aqueous solution to 40-60 ℃, sequentially adding aminopropylamine dioleate quaternary ammonium salt with the mass of 0.7-1.1% of the sodium hydroxide aqueous solution at 6000-9000 rpm, DY-ET113 hydrophilic reactive polyether modified polysiloxane with the mass of 0.3-0.5%, THI S-S30 alkaline silica sol with the mass of 4-8% and chitosan-coated lily dry powder microsphere with the mass of 3-7%, stirring and dispersing for 2-4 hours to obtain the chitosan-coated lily dry powder microsphere dispersion liquid;
the preparation of the blending spinning solution, which is to take cellulose pulp as a raw material, obtain a yellowing product through the steps of dipping, squeezing, crushing, ageing and yellowing, and dissolve the yellowing product in the dispersion of chitosan-coated lily dry powder microspheres according to the mass ratio of the yellowing product to the dispersion of chitosan-coated lily dry powder microspheres of 1:2-4 to obtain the blending spinning solution; the blend spinning solution comprises 8.8wt% of alpha cellulose, the viscosity is 53s and the maturity is 9.9% NH 4 Cl value was 18mL.
2. The macrobiose viscose fiber containing lily active ingredient according to claim 1, wherein: the addition amount of the chitosan is 6-10% of the mass of the acetic acid solution with the weight percent of 1%; the concentration of the sodium hydroxide aqueous solution is 0.1mol/L; the concentration of the sodium pyrophosphate aqueous solution is 0.6-0.8 g/L, and the addition amount is 12-15% of the mass of the acetic acid solution with the weight percent of 1.
3. The macrobiose viscose fiber containing lily active ingredient according to claim 1, wherein:
the preparation of the lily dry powder, namely adding deionized water with the mass of 0.5-0.8 times of that of the fresh lily into the fresh lily, beating the fresh lily into slurry at 10000-20000 revolutions per minute, drying the obtained slurry at 40-60 ℃ under the pressure of-0.04 to-0.09 MPa for 60-80 minutes under the condition that the slurry thickness is 0.5-1.5 cm to obtain solid with the moisture content of 0.5-1.3%, and then dry-grinding the solid at 20000-35000 revolutions per minute to obtain the lily dry powder with the particle size of 0.1-0.5 microns.
4. The macrobiose viscose fiber containing lily active ingredient according to claim 1, wherein: the spinning and post-treatment, filtering and defoaming blended spinning liquid, spraying fine flow through a nozzle of a spinning machine to form tows, feeding the tows into a second bath by a first drafting machine, feeding the tows into a third bath by a second drafting machine after the second bath, and feeding the tows after the third bath into the post-treatment by a third drafting machine, wherein the post-treatment is to desulfurize, bleach and oil the drafted tows.
5. The macrobiose viscose fiber containing lily active ingredient according to claim 4, wherein: the coagulation bath used in the first bath is 100-125 g/L sulfuric acid, 200-260 g/L sodium sulfate and 12-16 g/L zinc sulfate, the first bath temperature is 45-55 ℃, and the draft rate of the first draft machine is 55-75%; the coagulating bath used in the second bath is 16-24 g/L sulfuric acid, the temperature of the second bath is 75-90 ℃, and the draft rate of the second drafting machine is 35-45%;
the coagulation bath used in the three baths is sulfuric acid with pH=1.5-2.5, the temperature of the three baths is 80-90 ℃, and the drafting rate of the three drafting machines is 6-12%.
6. The macrobiose viscose fiber containing lily active ingredient according to claim 4, wherein: the desulfurizing agent consists of sodium sulfide with the concentration of 3-7 g/L and sodium carbonate with the concentration of 2-5 g/L; the bleaching agent used in the bleaching is hydrogen peroxide with the concentration of 0.2-0.4 g/L; the adding amount of the oiling agent is 5-8 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111343162.1A CN113832562B (en) | 2021-11-13 | 2021-11-13 | Large biological viscose fiber containing lily active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111343162.1A CN113832562B (en) | 2021-11-13 | 2021-11-13 | Large biological viscose fiber containing lily active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113832562A CN113832562A (en) | 2021-12-24 |
| CN113832562B true CN113832562B (en) | 2023-05-09 |
Family
ID=78971206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111343162.1A Active CN113832562B (en) | 2021-11-13 | 2021-11-13 | Large biological viscose fiber containing lily active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113832562B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846463A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Extinction type low-elongation viscose fiber and preparation method and application thereof |
| CN106498528A (en) * | 2016-10-20 | 2017-03-15 | 安徽依采妮纤维材料科技有限公司 | A kind of preparation method of Chinese herbal medicine aroma type viscose rayon |
| CN106591990B (en) * | 2016-12-12 | 2019-07-09 | 浙江三佳制衣有限公司 | A kind of more effect regenerated celulose fibres |
-
2021
- 2021-11-13 CN CN202111343162.1A patent/CN113832562B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113832562A (en) | 2021-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108588880B (en) | Preparation method of clean high-whiteness viscose fiber | |
| CN108588894A (en) | The preparation method and applications of the mould proof regenerated celulose fibre of antibiosis anti-acarien | |
| CN110791830A (en) | Multifunctional viscose fiber containing plant extract, preparation method thereof and obtained non-woven fabric | |
| CN103981588A (en) | Antibacterial and deodorization cellulosic fiber and preparation method thereof | |
| CN107955988B (en) | Preparation method of viscose containing chitin | |
| CN100507100C (en) | Calamine viscose fiber and preparation method and application thereof | |
| CN112210846A (en) | Preparation method of plant antibacterial, antiviral, skin-care and health-care cellulose fiber | |
| CN105839408A (en) | Preparation method of bamboo fiber-cotton and ramie blended fabric | |
| CN110965149A (en) | Water lily protein fiber and preparation process thereof | |
| CN109610026A (en) | One kind regenerated celulose fibre containing essential oil and preparation method thereof | |
| CN115044992A (en) | Preparation method of viscose macrobio-fiber containing seaweed active ingredients | |
| CN112144144A (en) | Alginate/cellulose composite fiber with flame retardant function and preparation method thereof | |
| CN105780234A (en) | Preparation method of composite yarns | |
| CN116837476A (en) | Durable antibacterial regenerated cellulose fiber and preparation method thereof | |
| TW201938858A (en) | Lyocell fiber with increased tendency to fibrillate | |
| CN113981557A (en) | Milk tea short fiber and preparation method thereof | |
| CN112359459B (en) | Preparation method of non-uniform yarn towel | |
| CN113832562B (en) | Large biological viscose fiber containing lily active ingredient | |
| CN112813518A (en) | Viscose macrobio-fiber containing active ingredients of tangerine peel, orange and pomelo and preparation method thereof | |
| CN110172741A (en) | A kind of preparation method of functional fiber element fiber | |
| CN112921650A (en) | High-elasticity antibacterial fabric and preparation method and application thereof | |
| CN112323165A (en) | Preparation method of hemp tea fiber | |
| CN114921865B (en) | Regenerated cellulose fiber containing nanometer particles of extracts of avocado and shea and preparation method thereof | |
| CN105951268A (en) | Cotton and hemp composite functional fabric | |
| CN115613359A (en) | Antibacterial protein modified viscose fiber and manufacturing process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |