CN108221081B - High-strength carboxymethyl cellulose/sodium alginate blend fiber and preparation method thereof - Google Patents
High-strength carboxymethyl cellulose/sodium alginate blend fiber and preparation method thereof Download PDFInfo
- Publication number
- CN108221081B CN108221081B CN201711329415.3A CN201711329415A CN108221081B CN 108221081 B CN108221081 B CN 108221081B CN 201711329415 A CN201711329415 A CN 201711329415A CN 108221081 B CN108221081 B CN 108221081B
- Authority
- CN
- China
- Prior art keywords
- sodium alginate
- preparation
- strength
- bath
- coagulating
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
- D06M2101/08—Esters or ethers of cellulose
Abstract
The invention relates to a high-strength carboxymethyl cellulose/sodium alginate blend fiber and a preparation method thereof. The preparation method of the high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps: (1) preparing a blended spinning solution; (2) adding sodium dodecyl sulfate and mixing; (3) filtering, defoaming, and coagulating by three coagulating baths; (4) carrying out fourth drafting after washing from the water bath; (5) soaking the water-washed blended fiber obtained in the step (4) in a glucose aqueous solution with the mass concentration of 20-30% for 10-15 minutes; (6) and (5) drying and winding. The invention improves the strength and spinnability of the alginate fiber by improving the preparation process, and enlarges the application range of the carboxymethyl cellulose/sodium alginate blend fiber.
Description
Technical Field
The invention relates to the technical field of fiber manufacturing, in particular to a high-strength carboxymethyl cellulose/sodium alginate blend fiber and a preparation method of the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
Background
The Alginic acid monomer is β -1, 4-D-mannuronic acid (M) and α -1, 4-L-guluronic acid (G), and Alginic acid is generally utilized in the form of alginate, such as sodium alginate, calcium alginate and the like, because of good biodegradability and biocompatibility, and high hygroscopicity and gelling property of Alginic acid fiber, the Alginic acid fiber is widely applied to the fields of chemistry, biology, medicine, food and the like, and is widely applied to the preparation of membrane materials with multiple purposes due to good film forming property.
However, the sodium alginate film is brittle, the fiber strength is not high, the spinnability is poor, the water resistance is extremely poor, and the application is limited. Most fibers obtained from the sodium carboxymethylcellulose raw material have low strength, and the obtained product has poor post-processing performance. At present, the blended fiber of sodium carboxymethyl cellulose and sodium alginate is prepared in China, and the process is that a spinning solution is extruded from a spinning nozzle through a wet spinning process, enters a calcium chloride coagulation bath, and is subjected to drafting, water washing, drying and winding to obtain the blended fiber. It mainly has the following disadvantages: the viscosity among the fibers is high, the spinnability is poor, and the fiber strength is not high.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for preparing high strength carboxymethylcellulose/sodium alginate blend fiber, which improves the strength and spinnability of alginate fiber by improving the preparation process.
In order to solve the technical problems, the invention adopts the following technical scheme that the preparation method of the high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate in deionized water according to the weight ratio of 1:2-10, and stirring for 2-3 hours to obtain a spinning solution;
(2) placing the spinning solution to 0-4 ℃, standing and preserving for 6-10 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 20-30 minutes at 40-50 ℃ under the condition of 200 and 300r/min, then adding sodium dodecyl sulfate, continuing to placing the spinning solution into the water bath shaking pot at 40-50 ℃ under the condition of 200 and 300r/min, and shaking for 50-60 minutes, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 20-30 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 1-2%, the coagulating temperature of the first coagulating bath is 50-55 ℃, and the coagulating time is 2-3 minutes; washing with 10% by mass of sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water at a ratio of 3-4:1:2, the coagulation temperature of the second coagulation bath is 20-30 ℃, and the coagulation time is 1-3 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 8-10%, the temperature of the third coagulating bath is 25-30 ℃, and the coagulating time is 3-4 minutes;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then drafting for the fourth time;
(5) soaking the water-washed blended fiber obtained in the step (4) in a glucose aqueous solution with the mass concentration of 20-30% for 10-15 minutes;
(6) and (4) drying and winding the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method has better hygroscopicity, and the liquid absorption amount of distilled water is 22-25g/g fiber, so that the high-strength carboxymethyl cellulose/sodium alginate blend fiber can better absorb wound penetrating fluid. The blended fiber can relieve edema and wound surface stimulation after operation, the bacterial packing is increased, the wound adhesion degree is smaller, the wound is easier to heal, and the secondary injury to the wound caused by wound adhesion is not easy to occur when the blended fiber is removed. In addition, the high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the invention has high breaking strength, and the fiber breaking strength is 2.6-3.1 cN/dtex. In addition, the preparation process reduces the viscosity between fibers, and solves the problem of poor spinnability of carboxymethyl cellulose/sodium alginate in the prior art. The treatment in the step (2) is beneficial to reducing the viscosity of the spinning solution, increasing the spinnability, improving the dispersibility and increasing the compatibility of the carboxymethyl cellulose and the sodium alginate. In the step (4), ions existing in the coagulation bath on the surface of the fiber can be washed away by the water washing bath. The blended fibers can be further modified through the treatment in the step (5), so that the viscosity among the fibers can be reduced, and the problem of poor spinnability of the carboxymethyl cellulose/sodium alginate in the prior art is solved. Therefore, the moisture absorption of the blended fiber is obviously enhanced, and the prepared blended fiber has high strength, low viscosity among fibers and high spinnability.
Further, in the step (1), the mass fraction of the sodium alginate in the carboxymethylcellulose/sodium alginate blended spinning solution is 6-15%, preferably 8-10%.
Further, the molecular weight of the sodium alginate is 300000-400000, and the M/G value is 2-2.5.
Furthermore, the draft multiple of the first draft of the fiber is 1-2 times, the draft multiple of the second draft is 1-1.5 times, the draft multiple of the third draft is 2-3 times, and the draft multiple of the fourth draft is 1-1.5 times.
Preferably, the spinning mixed solution in the step (1) further comprises plant essential oil, the amount of the plant essential oil is 0.5-1.0% of the mass of the sodium alginate, and the plant essential oil can be rose essential oil.
Preferably, the spinning mixed solution in the step (1) further comprises an antibacterial agent, the dosage of the antibacterial agent is 0.5-1.0% of the mass of the sodium alginate, and the antibacterial agent can be honeysuckle extract or cortex moutan decoction.
Further, the drying method of the step (6) is drying at 60 ℃.
Further, the drying method of the step (6) is vacuum freeze drying. Its advantages are high mechanical performance and three-dimensional porous structure of alginate fibres.
The invention also discloses the high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
The invention also discloses application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in manufacturing medical sanitary dressings.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the ratio and the mixing method of the carboxymethyl cellulose and the sodium alginate are improved, and the preparation processes of components of a coagulating bath, temperature, coagulation time of fibers and the like are improved, so that the strength and spinnability of the alginate fibers are improved, the viscosity among the fibers is reduced, the processing difficulty of the blend fibers is reduced, the hygroscopicity of the blend fibers is improved, and the application range of the carboxymethyl cellulose/sodium alginate blend fibers is expanded.
(2) The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method has better hygroscopicity, so that the wound penetrating fluid can be better absorbed. The blended fiber can relieve edema and wound surface stimulation after operation, the bacterial packing is increased, the wound adhesion degree is smaller, the wound is easier to heal, and the secondary injury to the wound caused by wound adhesion is not easy to occur when the blended fiber is removed.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified.
Example 1
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate into deionized water according to the weight ratio of 1:2, and stirring for 3 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate in the spinning solution is 12%;
(2) placing the spinning solution to 0 ℃, standing and preserving for 8 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 30 minutes at 40 ℃ at 300r/min, then adding sodium dodecyl sulfate, and continuing to shake for 50 minutes at 40 ℃ at 300r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 25 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 2%, the coagulating temperature of the first coagulating bath is 50 ℃, and the coagulating time is 2 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water in a ratio of 3:1:2, the coagulation temperature of the second coagulation bath is 25 ℃, and the coagulation time is 2 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 8%, the temperature of the third coagulating bath is 28 ℃, and the coagulating time is 4 minutes;
the draft multiple of the first draft of the fiber is 1 time, the draft multiple of the second draft is 1.5 times, and the draft multiple of the third draft is 2 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1.5 times;
(5) soaking the water-washed blended fiber obtained in the step (4) in a 24% glucose aqueous solution for 15 minutes;
(6) and (4) performing vacuum freeze drying and winding on the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
Example 2
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate into deionized water according to the weight ratio of 1:4, and stirring for 2 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate in the spinning solution is 10%;
(2) placing the spinning solution to 0 ℃, standing and preserving for 6 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 20 minutes at 45 ℃ at 200r/min, then adding sodium dodecyl sulfate, and continuing to shake for 60 minutes at 45 ℃ at 200r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 20 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 1%, the coagulating temperature of the first coagulating bath is 55 ℃, and the coagulating time is 3 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water at a ratio of 4:1:2, the coagulation temperature of the second coagulation bath is 20 ℃, and the coagulation time is 2 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 9%, the temperature of the third coagulating bath is 25 ℃, and the coagulating time is 4 minutes;
the draft multiple of the first draft of the fiber is 1.5 times, the draft multiple of the second draft is 1 time, and the draft multiple of the third draft is 3 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1.2 times;
(5) soaking the water-washed blend fiber obtained in the step (4) in a 30% glucose aqueous solution for 12 minutes;
(6) and (4) performing vacuum freeze drying and winding on the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
Example 3
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate into deionized water according to the weight ratio of 1:5, and stirring for 3 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate is 10%;
(2) placing the spinning solution to 2 ℃, standing and preserving for 8 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 20 minutes at 48 ℃ at 300r/min, then adding sodium dodecyl sulfate, and continuing to shake for 60 minutes at 45 ℃ at 300r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 25 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 2%, the coagulating temperature of the first coagulating bath is 55 ℃, and the coagulating time is 2 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water in a ratio of 3:1:2, the coagulation temperature of the second coagulation bath is 30 ℃, and the coagulation time is 2 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 9%, the temperature of the third coagulating bath is 28 ℃, and the coagulating time is 3 minutes;
the draft multiple of the first draft of the fiber is 2 times, the draft multiple of the second draft is 1 time, and the draft multiple of the third draft is 2.5 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1 time;
(5) soaking the water-washed blend fiber obtained in the step (4) in a 30% glucose aqueous solution for 12 minutes;
(6) and (4) performing vacuum freeze drying and winding on the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
Example 4
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate into deionized water according to the weight ratio of 1:5, and stirring for 2 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate in the spinning solution is 8%;
(2) placing the spinning solution to 4 ℃, standing and preserving for 10 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 30 minutes at 45 ℃ at 250r/min, then adding sodium dodecyl sulfate, and continuing to shake for 50 minutes at 45 ℃ at 250r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 30 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 1%, the coagulating temperature of the first coagulating bath is 50 ℃, and the coagulating time is 3 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water in a ratio of 3:1:2, the coagulation temperature of the second coagulation bath is 28 ℃, and the coagulation time is 2 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 10%, the temperature of the third coagulating bath is 30 ℃, and the coagulating time is 3 minutes;
the draft multiple of the first draft of the fiber is 1.5 times, the draft multiple of the second draft is 1.2 times, and the draft multiple of the third draft is 2 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1.2 times;
(5) soaking the water-washed blend fiber obtained in the step (4) in a 30% glucose aqueous solution for 10 minutes;
(6) and (4) performing vacuum freeze drying and winding on the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
Example 5
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate in deionized water according to the weight ratio of 1:6, and stirring for 3 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate in the spinning solution is 9%;
(2) placing the spinning solution to 4 ℃, standing and preserving for 6 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 30 minutes at 48 ℃ at 200r/min, then adding sodium dodecyl sulfate, and continuing to shake for 50 minutes at 50 ℃ at 300r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 25 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 2%, the coagulating temperature of the first coagulating bath is 55 ℃, and the coagulating time is 3 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water in a ratio of 3:1:2, the coagulation temperature of the second coagulation bath is 20 ℃, and the coagulation time is 1 minute; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride water solution with the mass fraction of 8%, the temperature of the third coagulating bath is 30 ℃, and the coagulating time is 4 minutes;
the draft multiple of the first draft of the fiber is 1.5 times, the draft multiple of the second draft is 1.5 times, and the draft multiple of the third draft is 2.5 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1.5 times;
(5) soaking the water-washed blend fiber obtained in the step (4) in a 25% glucose aqueous solution for 15 minutes;
(6) and (4) performing vacuum freeze drying and winding on the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
Example 6
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate into deionized water according to the weight ratio of 1:8, and stirring for 2 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate in the spinning solution is 6%;
(2) placing the spinning solution to 3 ℃, standing and preserving for 7 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 25 minutes at 50 ℃ at 200r/min, then adding sodium dodecyl sulfate, and continuing to shake for 50 minutes at 45 ℃ at 240r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 20 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 2%, the coagulating temperature of the first coagulating bath is 50 ℃, and the coagulating time is 2 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water at a ratio of 4:1:2, the coagulation temperature of the second coagulation bath is 30 ℃, and the coagulation time is 3 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 10%, the temperature of the third coagulating bath is 30 ℃, and the coagulating time is 3 minutes;
the draft multiple of the first draft of the fiber is 2 times, the draft multiple of the second draft is 1 time, and the draft multiple of the third draft is 2 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1.2 times;
(5) soaking the water-washed blended fiber obtained in the step (4) in a 20% glucose aqueous solution for 15 minutes;
(6) and (4) performing vacuum freeze drying and winding on the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
Example 7
A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate into deionized water according to the weight ratio of 1:10, and stirring for 3 hours to obtain a spinning solution, wherein the mass fraction of the sodium alginate in the spinning solution is 15%;
(2) placing the spinning solution to 2 ℃, standing and preserving for 8 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 20 minutes at 40 ℃ under the condition of 300r/min, then adding sodium dodecyl sulfate, and continuing to shake for 60 minutes at 50 ℃ under the condition of 200r/min in the water bath shaking pot, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 30 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 1%, the coagulating temperature of the first coagulating bath is 55 ℃, and the coagulating time is 2 minutes; washing with a 10% sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water at a ratio of 4:1:2, the coagulation temperature of the second coagulation bath is 25 ℃, and the coagulation time is 1 minute; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride water solution with the mass fraction of 8%, the temperature of the third coagulating bath is 30 ℃, and the coagulating time is 4 minutes;
the draft multiple of the first draft of the fiber is 1 time, the draft multiple of the second draft is 1.2 times, and the draft multiple of the third draft is 3 times;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then performing fourth drafting, wherein the drafting multiple of the fourth drafting is 1 time;
(5) soaking the water-washed blend fiber obtained in the step (4) in a 30% glucose aqueous solution for 10 minutes;
(6) and (4) drying and winding the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber.
The high-strength carboxymethyl cellulose/sodium alginate blend fiber prepared by the preparation method.
An application of the high-strength carboxymethyl cellulose/sodium alginate blend fiber in the preparation of medical sanitary dressing.
The high strength carboxymethylcellulose/sodium alginate blend fibers prepared in examples 1-7 were subjected to performance measurement.
Measurement of liquid absorption amount: weighing 0.1g of blended fiber sample, and soaking in 50mL of distilled water for 30 min; centrifuging and dehydrating the fiber after water absorption for 15min, wherein the rotating speed of a centrifuge is 2000r/min, weighing, and recording the mass as M1; the fiber was then placed in an oven at 105 ℃ to a constant weight, weighed, and the mass recorded as M2. The liquid absorption amount of the fiber was (M1-M2)/M2. The results showed that the high-strength carboxymethylcellulose/sodium alginate blend fibers obtained in examples 1 to 7 had a liquid absorption of distilled water of 22 to 25g/g fiber. Therefore, the liquid absorption amount of the invention is obviously improved, and the wound penetrating fluid can be better absorbed.
And (3) determination of breaking strength: the breaking strength of the high-strength carboxymethylcellulose/sodium alginate blended fiber prepared in the examples 1 to 7 is determined by referring to GB/T14337-.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (8)
1. A preparation method of high-strength carboxymethyl cellulose/sodium alginate blend fiber is characterized in that: the method comprises the following steps:
(1) preparation of blended spinning solution: dissolving carboxymethyl cellulose and sodium alginate in deionized water according to the weight ratio of 1:2-10, and stirring for 2-3 hours to obtain a spinning solution;
(2) placing the spinning solution to 0-4 ℃, standing and preserving for 6-10 hours, taking out, placing the spinning solution into a water bath shaking pot, shaking for 20-30 minutes at 40-50 ℃ under the condition of 200 and 300r/min, then adding sodium dodecyl sulfate, continuing to placing the spinning solution into the water bath shaking pot at 40-50 ℃ under the condition of 200 and 300r/min, and shaking for 50-60 minutes, wherein the addition amount of the sodium dodecyl sulfate is 1 percent of the mass of the sodium alginate;
(3) putting the mixed solution obtained in the step (2) into an ultrasonic mixer for ultrasonic mixing for 20-30 minutes, pouring the mixed spinning solution into a dissolving kettle for filtering and defoaming, then extruding the mixed spinning solution into a first coagulating bath from a spinneret plate through a metering pump, and carrying out first drafting, wherein the first coagulating bath is a calcium chloride aqueous solution with the mass fraction of 1-2%, the coagulating temperature of the first coagulating bath is 50-55 ℃, and the coagulating time is 2-3 minutes; washing with 10% by mass of sodium hydroxide aqueous solution after primary drawing, introducing into a second coagulation bath, and performing secondary drawing, wherein the second coagulation bath is prepared from ethanol, methanol and deionized water at a ratio of 3-4:1:2, the coagulation temperature of the second coagulation bath is 20-30 ℃, and the coagulation time is 1-3 minutes; washing with deionized water after the second drafting, introducing into a third coagulating bath, and drafting for the third time, wherein the third coagulating bath is a calcium chloride aqueous solution with the mass fraction of 8-10%, the temperature of the third coagulating bath is 25-30 ℃, and the coagulating time is 3-4 minutes;
(4) washing the fiber after the three coagulating baths from a water washing bath, and then drafting for the fourth time;
(5) soaking the water-washed blended fiber obtained in the step (4) in a glucose aqueous solution with the mass concentration of 20-30% for 10-15 minutes;
(6) drying and winding the soaked blend fiber obtained in the step (5) to obtain the high-strength carboxymethyl cellulose/sodium alginate blend fiber;
in the step (1), the mass fraction of sodium alginate in the carboxymethyl cellulose/sodium alginate blended spinning solution is 6-15%; the molecular weight of the sodium alginate is 300000-400000, and the M/G value is 2-2.5.
2. The preparation method of the high-strength carboxymethylcellulose/sodium alginate blend fiber according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the mass fraction of the sodium alginate in the carboxymethyl cellulose/sodium alginate blended spinning solution is 8-10%.
3. The preparation method of the high-strength carboxymethylcellulose/sodium alginate blend fiber according to claim 1, wherein the preparation method comprises the following steps: the draft multiple of the first draft of the fiber is 1-2 times, the draft multiple of the second draft is 1-1.5 times, the draft multiple of the third draft is 2-3 times, and the draft multiple of the fourth draft is 1-1.5 times.
4. The preparation method of the high-strength carboxymethylcellulose/sodium alginate blend fiber according to claim 1, wherein the preparation method comprises the following steps: the spinning mixed solution in the step (1) also comprises plant essential oil, and the using amount of the plant essential oil is 0.5-1.0% of the mass of the sodium alginate.
5. The preparation method of the high-strength carboxymethylcellulose/sodium alginate blend fiber according to claim 1, wherein the preparation method comprises the following steps: the spinning mixed solution in the step (1) also comprises an antibacterial agent, and the dosage of the antibacterial agent is 0.5-1.0% of the mass of the sodium alginate.
6. The preparation method of the high-strength carboxymethylcellulose/sodium alginate blend fiber according to claim 1, wherein the preparation method comprises the following steps: the drying method of the step (6) is vacuum freeze drying.
7. A blended fiber prepared by the preparation method of the high-strength carboxymethylcellulose/sodium alginate blended fiber according to any one of claims 1 to 6.
8. An application of the high-strength carboxymethylcellulose/sodium alginate blend fiber as defined in claim 7 in the preparation of medical sanitary dressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711329415.3A CN108221081B (en) | 2017-12-13 | 2017-12-13 | High-strength carboxymethyl cellulose/sodium alginate blend fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711329415.3A CN108221081B (en) | 2017-12-13 | 2017-12-13 | High-strength carboxymethyl cellulose/sodium alginate blend fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108221081A CN108221081A (en) | 2018-06-29 |
| CN108221081B true CN108221081B (en) | 2020-05-26 |
Family
ID=62652258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711329415.3A Active CN108221081B (en) | 2017-12-13 | 2017-12-13 | High-strength carboxymethyl cellulose/sodium alginate blend fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108221081B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914389A (en) * | 2018-07-11 | 2018-11-30 | 高昕文 | A kind of preparation method of composite fibre spunlaced face mask base fabric |
| CN109137502A (en) * | 2018-08-07 | 2019-01-04 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of moisture absorbing and sweat releasing knitting fabric |
| CN109627498A (en) * | 2018-11-27 | 2019-04-16 | 青岛大学 | A kind of sodium alginate-cellulose derivative blended membrane/fiber and preparation method thereof |
| CN109868525A (en) * | 2019-02-19 | 2019-06-11 | 青岛海赛尔新材料科技有限公司 | A kind of preparation method of high intensity seaweed and polyvinyl alcohol blending fiber |
| CN109972233A (en) * | 2019-02-19 | 2019-07-05 | 青岛大学 | The preparation method of the biodegradable alginic acid fibre with high-intensity and high-tenacity |
| CN110241481A (en) * | 2019-05-28 | 2019-09-17 | 福建美可纸业有限公司 | A kind of superabsorbent water composite fibre and preparation method thereof |
| CN112127009B (en) * | 2020-09-11 | 2022-10-14 | 嘉兴学院 | Cellulose/calcium alginate blend fiber with skin-core structure and preparation method thereof |
| CN116730691A (en) * | 2023-05-25 | 2023-09-12 | 东莞市欧丽亚环保材料有限公司 | Ceramic tile adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060946A (en) * | 2012-12-21 | 2013-04-24 | 稳健实业(深圳)有限公司 | Blend fibers of alginate and sodium carboxymethyl cellulose and preparation method and application thereof |
| CN105544002A (en) * | 2015-12-18 | 2016-05-04 | 厦门百美特生物材料科技有限公司 | Superabsorbent composite fiber and preparation method thereof |
| CN106702533A (en) * | 2015-07-27 | 2017-05-24 | 吴玉松 | High-strength alginate composite fiber, and preparation method and use thereof |
| WO2017085436A1 (en) * | 2015-11-18 | 2017-05-26 | Advanced Medical Solutions Limited | Gelling fibres |
| CN106894111A (en) * | 2017-03-30 | 2017-06-27 | 广东泰宝医疗科技股份有限公司 | A kind of preparation method of the compound alginate dressing of soft moisture absorption |
-
2017
- 2017-12-13 CN CN201711329415.3A patent/CN108221081B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060946A (en) * | 2012-12-21 | 2013-04-24 | 稳健实业(深圳)有限公司 | Blend fibers of alginate and sodium carboxymethyl cellulose and preparation method and application thereof |
| CN106702533A (en) * | 2015-07-27 | 2017-05-24 | 吴玉松 | High-strength alginate composite fiber, and preparation method and use thereof |
| WO2017085436A1 (en) * | 2015-11-18 | 2017-05-26 | Advanced Medical Solutions Limited | Gelling fibres |
| CN105544002A (en) * | 2015-12-18 | 2016-05-04 | 厦门百美特生物材料科技有限公司 | Superabsorbent composite fiber and preparation method thereof |
| CN106894111A (en) * | 2017-03-30 | 2017-06-27 | 广东泰宝医疗科技股份有限公司 | A kind of preparation method of the compound alginate dressing of soft moisture absorption |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108221081A (en) | 2018-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108221081B (en) | High-strength carboxymethyl cellulose/sodium alginate blend fiber and preparation method thereof | |
| CN103060946B (en) | Blend fibers of alginate and sodium carboxymethyl cellulose and preparation method and application thereof | |
| CN107447297B (en) | A kind of hydrogel alginate fibre and preparation method thereof | |
| KR102133237B1 (en) | Method for manufacturing regenerated cellulose fibers having antibacterial, anti-mite and antifungal functions and uses thereof | |
| CN105011391B (en) | A kind of natural antibacterial bamboo fiber socks | |
| CN106283270B (en) | A kind of aquogel type alginate fibre and preparation method thereof | |
| CN103055344B (en) | Bacterial cellulose/chitosan composite medical dressing and preparation method thereof | |
| CN103806123A (en) | Silk fibroin/sodium alginate composite fiber and preparation method thereof | |
| CN101700409A (en) | Material prepared from purely natural material and used for wounds | |
| WO2014044011A1 (en) | Alginate woven fabrics and method for preparing the same | |
| CN103132179A (en) | Method for preparing alginate fiber | |
| CN109627498A (en) | A kind of sodium alginate-cellulose derivative blended membrane/fiber and preparation method thereof | |
| CN106110383A (en) | A kind of chitosan alginate dressing and freeze-drying process thereof | |
| CN107325303B (en) | Degumming-free silk fiber solution, preparation method and application thereof | |
| CN108018620B (en) | Antibacterial zirconium sodium silver phosphate alginate fiber and preparation method thereof | |
| CN102912474B (en) | Composite fiber and preparation method thereof | |
| CN109252245B (en) | Super-absorbent alginate fiber and preparation method thereof | |
| CN101368328B (en) | Preparation method for hydroxyethyl group chitosan fiber | |
| CN105153458A (en) | Preparation method for low-water-solubility bletilla striata polysaccharide porous membrane | |
| CN107385910A (en) | Fiber composite natral Anti-bacterial and Crease agent and preparation method thereof | |
| CN1157355A (en) | Styptic fibre composition and its air-drawing process | |
| CN114949329B (en) | Preparation method of surface modified silk fibroin-aloin double-layer fiber membrane | |
| CN109234836A (en) | A kind of poly- polysaccharide composite fiber of homogeneous and preparation method thereof | |
| CN112626631B (en) | Sea-buckthorn fiber and preparation method thereof | |
| CN111394818B (en) | Liquorice regenerated cellulose fiber and preparation method 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 |