CN110607570A - Medical absorbable biomaterial filament - Google Patents
Medical absorbable biomaterial filament Download PDFInfo
- Publication number
- CN110607570A CN110607570A CN201910930376.5A CN201910930376A CN110607570A CN 110607570 A CN110607570 A CN 110607570A CN 201910930376 A CN201910930376 A CN 201910930376A CN 110607570 A CN110607570 A CN 110607570A
- Authority
- CN
- China
- Prior art keywords
- crosslinking
- liquid
- filament
- collagen
- raw material
- 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.)
- Pending
Links
Classifications
-
- 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
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
-
- 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
-
- 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
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
-
- 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
- D06M2101/10—Animal fibres
- D06M2101/14—Collagen fibres
Abstract
The invention discloses a medical absorbable biomaterial filament, which is prepared by uniformly stirring collagen raw materials in acidic liquid, filtering to remove particle impurities and gas to obtain raw material liquid, injecting the raw material liquid into coagulating liquid by using a wet spinning technology to shape the raw material liquid, and then carrying out air drying, twisting/or non-twisting and crosslinking processes to obtain the collagen filament. Its advantages are long length of collagen fibres, high strength of collagen fibres, and high absorbability of collagen filaments. The invention can obtain collagen filaments, can be made into various products according to market demands, and has the characteristics of low cost, convenient operation, degradability and absorption, no toxic or side effect, controllable fiber length and controllable strength.
Description
Technical Field
The invention relates to the technical field of medical instruments and 3D printing, in particular to a medical absorbable biomaterial filament.
Background
At present, in the technical field of long fibers of collagen products, solutions of the collagen products have different degrees of viscosities, so that the long fibers are difficult to manufacture, and short fibers or entangled long fibers can be obtained by long-time operation such as pH adjustment. In order to manufacture collagen filaments with certain length and strength and meet the requirements of markets on collagen multi-component products, the invention provides the collagen filaments with low investment, convenient operation, degradability and absorption, no toxic or side effect, controllable fiber length and controllable strength.
Disclosure of Invention
In view of the above, the invention provides a collagen filament with low cost, convenient operation, degradability and absorption, no toxic or side effect, controllable fiber length and controllable strength, and various clinically-required products such as silk threads, membranes, rolls, columns, spheres, blocks and the like can be prepared by using the collagen filament.
In order to achieve the purpose, the invention provides the following technical scheme:
a medical absorbable biomaterial filament, characterized by that, the raw material used can be pure collagen, compound of collagen and mucopolysaccharide or combination of collagen and chitosan; uniformly stirring the raw materials by using an acid solution, filtering to remove particle impurities and gas to obtain a raw material solution; injecting raw material liquid into coagulating liquid by using a wet spinning technology to obtain monofilaments, multifilaments or specific shapes; the solidification liquid is a mixture of alcohols, ketones and ammonia water; after shaping by a coagulating liquid, obtaining collagen filaments by airing, twisting or non-twisting and crosslinking processes; the length of the filament can be arbitrarily made according to the requirement; the strength of the filament can be freely made according to the requirement; the crosslinking process can adopt physical crosslinking, chemical crosslinking and physical-chemical crosslinking, and the crosslinking time is set according to the needs of the product; the obtained filament can be used for making products such as silk thread clothes, film, reel, column, ball and block.
In the above medical absorbable biomaterial filament, the raw material may be pure collagen, a compound of collagen and mucopolysaccharide, or a combination of a plurality of substances such as collagen and chitosan.
In the medical absorbable biomaterial filament, when the coagulating liquid is alcohol, the stirring time is 60-90 min; the most preferred stirring time is 20-80 min. The concentration of the alcohol is 50% -100%; when the solidification liquid is ketone, the concentration of the ketone is 70-100%; when the solidification liquid is a mixture of ketones and ammonia water, the volume ratio is as follows: ketones: ammonia water: 50-150% of water: 3-10: 0.5-1.5.
Preferably, in the medical absorbable biomaterial filament, the speed of injecting the raw material liquid into the coagulating liquid is 0.5-20 cm/s.
The preferred rate of injection of the raw material liquid into the coagulation liquid is 4 to 15cm/s, and the most preferred rate of injection of the raw material liquid into the coagulation liquid is 5 cm/s.
Preferably, in the above one medical absorbable biomaterial filament, the physical crosslinking method includes ultraviolet irradiation, thermal crosslinking; the chemical crosslinking method comprises aldehyde crosslinking, imine crosslinking, diisocyanate crosslinking, genipin crosslinking, azido diphenylphosphine crosslinking and procyanidine crosslinking; and physical-chemical crosslinking methods.
According to the technical scheme, the invention discloses a medical absorbable biomaterial filament, collagen raw materials are uniformly stirred in acidic liquid, particle impurities are removed through filtration, gas is removed, raw material liquid is obtained, the raw material liquid is injected into coagulating liquid through a wet spinning technology to be shaped, the collagen filament is obtained through processes of airing, twisting and crosslinking, and the obtained filament can be manufactured into products in various shapes such as thread shape, membrane shape, reel shape, column shape, sphere shape, block shape and the like according to clinical needs.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a method for manufacturing a medical absorbable biomaterial filament with low investment, convenient operation, degradability, absorption, no toxic or side effect, controllable fiber length and controllable strength.
Example 1: taking pure collagen as an example
Measuring 0.5M glacial acetic acid aqueous solution, adding collagen, stirring for 45min, and filtering to remove particle impurities.
And (II) removing redundant gas by adopting a vibration vacuumizing mode to obtain 0.6 percent of raw material liquid.
And (III) injecting the raw material solution into the coagulating liquid at the speed of 0.5cm/s, wherein the coagulating liquid is a 50% ethanol solution.
And (IV) after the injected monofilaments are shaped, taking out and airing to obtain long fibers.
And (V) twisting the long fibers to twist and wind a plurality of long fibers together to obtain a strand of long fibers.
And (VI) putting the filaments into glutaraldehyde gas for crosslinking, so as to improve the strength of the filaments.
And (seventhly) weaving the filaments by a weaving machine to obtain a film-shaped product, or obtaining products in other shapes by other weaving modes.
Example 2: taking pure collagen as an example
Measuring 0.5M glacial acetic acid aqueous solution, adding collagen, stirring for 75min, and filtering to remove particle impurities.
And (II) removing redundant gas by adopting a vibration vacuumizing mode to obtain 0.6 percent of raw material liquid.
And (III) injecting the raw material solution into a coagulating liquid at a speed of 5cm/s, wherein the coagulating liquid is a 75% ethanol solution.
And (IV) after the injected multifilaments are shaped, taking out and airing to obtain the filaments.
And (V) putting the filaments into glutaraldehyde gas for crosslinking, so as to improve the strength of the filaments.
And (VI) weaving the filaments by a weaving machine to obtain a film-shaped product, or obtaining products in other shapes by other weaving modes.
Example 3: taking pure collagen as an example
Measuring 0.5M glacial acetic acid aqueous solution, adding collagen, stirring for 90min, and filtering to remove particle impurities.
And (II) removing redundant gas by adopting a vibration vacuumizing mode to obtain 0.6 percent of raw material liquid.
And (III) injecting the raw material solution into the coagulating liquid at a speed of 10cm/s, wherein the coagulating liquid is an absolute ethyl alcohol solution.
And (IV) after the injected monofilaments are shaped, taking out and airing to obtain long fibers.
And (V) twisting the long fibers to twist and wind a plurality of long fibers together to obtain a strand of long fibers.
And (VI) putting the filaments into glutaraldehyde gas for crosslinking, so as to improve the strength of the filaments.
And (seventhly) weaving the filaments by a weaving machine to obtain a film-shaped product, or obtaining products in other shapes by other weaving modes.
Example 4: taking collagen and mucopolysaccharide complex as an example
Measuring 0.5M glacial acetic acid water solution, adding collagen, stirring for 30min, adding mucopolysaccharide (such as chondroitin sulfate), stirring for 30min, and filtering to remove particulate impurities.
And (II) removing redundant gas by adopting an ultrasonic mode to obtain 0.5 percent of raw material liquid.
(III) injecting the raw material liquid into the coagulating liquid at the speed of 0.5cm/s, wherein the injected raw material liquid is multifilament, and the coagulating liquid is ketone: ammonia water: 100 parts of water: 6: 1.
and (IV) after the injected multifilaments are shaped, taking out and airing to obtain the filaments.
And (V) crosslinking the filaments in a thermal crosslinking mode to improve the strength of the filaments.
And (VI) weaving the filaments by a weaving machine to obtain a film-shaped product, or obtaining products in other shapes by other weaving modes.
Example 5: taking collagen and mucopolysaccharide complex as an example
Measuring 0.5M glacial acetic acid water solution, adding collagen, stirring for 45min, adding mucopolysaccharide (such as chondroitin sulfate), stirring for 45min, and filtering to remove particulate impurities.
And (II) removing redundant gas by adopting an ultrasonic mode to obtain 0.5 percent of raw material liquid.
(III) injecting the raw material liquid into the coagulating liquid at the speed of 5cm/s, wherein the injected raw material liquid is multifilament, and the coagulating liquid is ketone: ammonia water: 100 parts of water: 8: 1.
and (IV) after the injected multifilaments are shaped, taking out and airing to obtain the filaments.
And (V) crosslinking the filaments in a thermal crosslinking mode to improve the strength of the filaments.
And (VI) weaving the filaments by a weaving machine to obtain a film-shaped product, or obtaining products in other shapes by other weaving modes.
Example 6: taking collagen and mucopolysaccharide complex as an example
Measuring 0.5M glacial acetic acid water solution, adding collagen, stirring for 80min, adding mucopolysaccharide (such as chondroitin sulfate), stirring for 80min, and filtering to remove particulate impurities.
And (II) removing redundant gas by adopting an ultrasonic mode to obtain 0.5 percent of raw material liquid.
(III) injecting the raw material liquid into the coagulating liquid at the speed of 10cm/s, wherein the injected raw material liquid is multifilament, and the coagulating liquid is ketone: ammonia water: 100 parts of water: 8: 1.
and (IV) after the injected multifilaments are shaped, taking out and airing to obtain the filaments.
And (V) crosslinking the filaments in a thermal crosslinking mode to improve the strength of the filaments.
And (VI) weaving the filaments by a weaving machine to obtain a film-shaped product, or obtaining products in other shapes by other weaving modes.
The embodiments in the present specification are described in an alternating and progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts between the embodiments may be alternated and referred to. For the matching method disclosed in the embodiment, since it corresponds to or intersects with the method disclosed in the embodiment, the description is simple, and for those skilled in the art, other methods can be obtained according to the provided method without creative efforts.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A medical absorbable biomaterial filament, its characterized in that: the raw material may be pure collagen, a complex of collagen and mucopolysaccharide, or a combination of various substances such as collagen and chitosan.
2. The medical absorbable biomaterial filament according to claim 1, wherein: soaking the raw materials in an acidic solution for 6h, stirring for 10-120min or directly stirring for 10-180min until uniform, filtering to remove particle impurities and remove gas to obtain 0.3% -1.0% raw material solution.
3. The medical absorbable biomaterial filament according to claim 2, wherein: the preferable stirring time is 30-90 min; the most preferred stirring time is 30-80 min.
4. The medical absorbable biomaterial filament according to claim 1, wherein:
(1) injecting raw material liquid into coagulating liquid by using a wet spinning technology to obtain monofilaments, multifilaments or specific shapes;
(2) the solidification liquid is a mixture of alcohols, ketones and ammonia water;
(3) after shaping by a coagulating liquid, obtaining collagen filaments by airing, twisting or non-twisting and crosslinking processes;
(4) the length of the filament can be arbitrarily made according to the requirement;
(5) the strength of the filament can be freely made according to the requirement;
(6) the crosslinking process can adopt physical crosslinking, chemical crosslinking and physical-chemical crosslinking, and the crosslinking time is set according to the needs of the product;
(7) the obtained filament can be used for making products such as silk thread clothes, film, reel, column, ball and block.
5. The medical absorbable biomaterial filament as claimed in claim 1, wherein the velocity of the raw material liquid injected into the coagulating liquid is 0.5-20 cm/s.
6. The medical absorbable biomaterial filament according to claim 5, wherein: the preferred rate of injection of the raw material liquid into the coagulation liquid is 4 to 15cm/s, and the most preferred rate of injection of the raw material liquid into the coagulation liquid is 5 cm/s.
7. The medical absorbable biomaterial filament according to claim 1, wherein the physical crosslinking method comprises ultraviolet irradiation, thermal crosslinking; the chemical crosslinking method comprises aldehyde crosslinking, imine crosslinking, diisocyanate crosslinking, genipin crosslinking, azido diphenylphosphine crosslinking and procyanidine crosslinking; and physical-chemical crosslinking methods.
8. A solidification liquid, when the solidification liquid is alcohol, the concentration of the alcohol is 50% -100%; when the solidification liquid is ketone, the concentration of the ketone is 70-100%; when the solidification liquid is a mixture of ketones and ammonia water, the volume ratio is as follows: ketones: ammonia water: 50-150% of water: 3-10: 0.5-1.5.
9. A solidification liquid as claimed in claim 8, wherein: the solidification liquid can also be used for solidification and shaping for manufacturing the medical absorbable material by a 3D printing technology.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910930376.5A CN110607570A (en) | 2019-09-29 | 2019-09-29 | Medical absorbable biomaterial filament |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910930376.5A CN110607570A (en) | 2019-09-29 | 2019-09-29 | Medical absorbable biomaterial filament |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110607570A true CN110607570A (en) | 2019-12-24 |
Family
ID=68893787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910930376.5A Pending CN110607570A (en) | 2019-09-29 | 2019-09-29 | Medical absorbable biomaterial filament |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110607570A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234104A (en) * | 2020-03-26 | 2020-06-05 | 四川大学 | Water-soluble cross-linking agent, preparation method thereof and prepared electro-spinning collagen fiber |
| CN113100983A (en) * | 2021-03-29 | 2021-07-13 | 青岛格诚经纬生物科技有限公司 | Biodegradable antibacterial health dental floss and production process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977912A (en) * | 2018-07-09 | 2018-12-11 | 天津工业大学 | The preparation method of collagenous fibres |
| CN109680350A (en) * | 2018-12-29 | 2019-04-26 | 无锡贝迪生物工程股份有限公司 | A kind of preparation method of collagen fabric |
| CN109821061A (en) * | 2019-01-18 | 2019-05-31 | 江南大学 | It is a kind of using collagen spinning and hyaluronic acid as the bionical gel of the adhesiveness of substrate |
| CN111501121A (en) * | 2019-01-31 | 2020-08-07 | 华北水利水电大学 | Method for preparing collagen fiber by wet spinning |
-
2019
- 2019-09-29 CN CN201910930376.5A patent/CN110607570A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977912A (en) * | 2018-07-09 | 2018-12-11 | 天津工业大学 | The preparation method of collagenous fibres |
| CN109680350A (en) * | 2018-12-29 | 2019-04-26 | 无锡贝迪生物工程股份有限公司 | A kind of preparation method of collagen fabric |
| CN109821061A (en) * | 2019-01-18 | 2019-05-31 | 江南大学 | It is a kind of using collagen spinning and hyaluronic acid as the bionical gel of the adhesiveness of substrate |
| CN111501121A (en) * | 2019-01-31 | 2020-08-07 | 华北水利水电大学 | Method for preparing collagen fiber by wet spinning |
Non-Patent Citations (2)
| Title |
|---|
| 张积财 等: "戊二醛交联改性鼠尾I 型胶原纤维的戊二醛交联改性鼠尾I 型胶原纤维的戊二醛交联改性鼠尾I 型胶原纤维的戊二醛交联改性鼠尾I 型胶原纤维的结构与性能研究", 《合成纤维工业》 * |
| 李倩 等: "胶原/高分子量壳聚糖复合纤维的制备及其性能, ，", 《纺织学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234104A (en) * | 2020-03-26 | 2020-06-05 | 四川大学 | Water-soluble cross-linking agent, preparation method thereof and prepared electro-spinning collagen fiber |
| CN113100983A (en) * | 2021-03-29 | 2021-07-13 | 青岛格诚经纬生物科技有限公司 | Biodegradable antibacterial health dental floss and production process thereof |
| CN113100983B (en) * | 2021-03-29 | 2022-03-15 | 青岛格诚经纬生物科技有限公司 | Biodegradable antibacterial health dental floss and production process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101492837B (en) | Process for producing bacteria cellulose fibre with high degree of polymerization | |
| Ozipek et al. | Wet spinning of synthetic polymer fibers | |
| JP6410815B2 (en) | Lyocell material for tobacco filter and production method thereof | |
| EP3241452B1 (en) | Lyocell material for cigarette filter, and preparation method therefor | |
| CN103215678B (en) | There is the method for making of natural antibacterial, deodorizing and anion function bamboo cellulose fibre | |
| EP3051011B1 (en) | Lyocell material for cigarette filter and method for preparing same | |
| CN101942705B (en) | Preparation method of regenerated bacterial cellulose fiber | |
| US9206528B2 (en) | Method and device for the production of molded bodies | |
| CN110607570A (en) | Medical absorbable biomaterial filament | |
| CN106048741B (en) | A kind of method that dry-wet spinning prepares cellulose fibre | |
| CN109610023A (en) | Lyocell fibers and its manufacturing method | |
| CN100503907C (en) | Method for direct manufacturing regenerated bamboo fiber from papermaking-level bamboo pulp dregs | |
| TWI619863B (en) | Method for preparing bamboo pulp cellulose non-woven fabric with deodorizing function | |
| KR102296584B1 (en) | Lyocell Material For Cigarette Filter and Method of the Same | |
| CN109680350A (en) | A kind of preparation method of collagen fabric | |
| TWI641734B (en) | Method for preparing bamboo pulp cellulose non-woven fabric with deodorizing function by spunbonding method | |
| ATE482306T1 (en) | CELLULOSE CARBAMAT SPINNING SOLUTION AND METHOD FOR PRODUCING A CELLULOSE CARBAMAT NON-WOVEN MATERIAL | |
| CN103820874A (en) | Preparation method of carboxy methylated cellulose-metal composition fibers | |
| CN110913724A (en) | Face pack paster | |
| KR101862855B1 (en) | Chitosan fiber ion bonded with AU and the manufacturing of the same | |
| CN104032399A (en) | Preparation method for acetate fiber through dry-wet process | |
| KR102157887B1 (en) | Crimped Lyocell Fiber | |
| KR101455006B1 (en) | Lyocell Material Cigarette Filter and Method for the Same | |
| CN1470679A (en) | Chitin nonwoven fabric and production method thereof | |
| CN105420925A (en) | Method for preparing cellulose non-woven fabric with mildew-proof, anti-bacterial and deodorant functions through electrostatic size spraying |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191224 |
|
| RJ01 | Rejection of invention patent application after publication |