CN111058146B - Woven fabric with heterochromatic effect and application thereof - Google Patents
Woven fabric with heterochromatic effect and application thereof Download PDFInfo
- Publication number
- CN111058146B CN111058146B CN201811207606.7A CN201811207606A CN111058146B CN 111058146 B CN111058146 B CN 111058146B CN 201811207606 A CN201811207606 A CN 201811207606A CN 111058146 B CN111058146 B CN 111058146B
- Authority
- CN
- China
- Prior art keywords
- woven fabric
- formic acid
- solution
- absorbance peak
- sample
- 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
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/02—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fibres, slivers or rovings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Abstract
The invention discloses a woven fabric with a heterochromatic effect and application thereof. The woven fabric is composed of cation dyeable nylon fibers and common nylon fibers, wherein the content of sulfonic acid groups in the cation dyeable nylon fibers is 500-1800 ppm; the difference between the absorbance peak value of the formic acid dissolving solution of the woven fabric and the absorbance peak value of the strong base-formic acid dissolving solution of the woven fabric is 0.001-0.300. Can be used for manufacturing sports clothes or casual clothes.
Description
Technical Field
The invention belongs to the field of textiles and materials, and particularly relates to a nylon woven fabric with a heterochromatic effect.
Background
Nylon fibers have excellent flexibility, elastic recovery, abrasion resistance, alkali resistance, moisture absorption, lightweight properties, and the like, and thus occupy an extremely important position in synthetic fibers. Nylon fibers are generally dyed by weak acid dyes and metal complex dyes, but fabrics dyed by the weak acid dyes are poor in fastness and not bright in color, heavy metal pollution exists in the production process of the metal complex dyes, and the dyed fabrics even can damage the skin, so that novel dyes capable of solving the problems are researched and developed, for example, a reactive dye for nylon dyeing is disclosed in patent document CN101709154A, the dye contains a specific structure, the dyeing quality can be greatly improved, the environment cannot be polluted, but only navy blue can be dyed, and the pursuit of consumers for attractive and novel clothes cannot be met.
Therefore, the heterochromatic fabric is produced at the same time. Patent document CN1756871A discloses a glittering fabric from polyamide yarns, comprising cationic dyeable nylon polymer yarns and acid dyeable nylon polymer yarns, the acid dyeable nylon polymer yarns having more than 35 amino terminal gram equivalents per 1000 kg of polymer, the glittering effect (two colors) being obtained by coloring in a single dyeing bath without the use of auxiliary chemicals to prevent cross contamination of acid dyes and cationic dyes, the surface of the resulting knitted fabric being capable of exhibiting a iridescent appearance, but this is only present on one side, is very restrictive, and does not meet the consumer's needs; further, no proposal has been made for improving the light resistance.
Disclosure of Invention
The invention aims to provide a woven fabric with a heterochromatic effect and good light resistance and application thereof.
The technical solution of the invention is as follows:
the woven fabric with the heterochromatic effect consists of cationic dyeable nylon fibers and common nylon fibers, wherein the content of sulfonic acid groups in the cationic dyeable nylon fibers is 500-1800 ppm; the difference between the absorbance peak value of the formic acid dissolving solution of the woven fabric and the absorbance peak value of the strong base-formic acid dissolving solution of the woven fabric is 0.001-0.300.
The woven fabric has different color effects on two surfaces and extremely excellent light resistance. Can be used for manufacturing sports clothes or leisure clothes and the like.
Detailed Description
The woven fabric with the heterochromatic effect consists of cationic dyeable nylon fibers and common nylon fibers, wherein the content of sulfonic acid groups in the cationic dyeable nylon fibers is 500-1800 ppm; the difference between the absorbance peak value of the formic acid dissolving solution of the woven fabric and the absorbance peak value of the strong base-formic acid dissolving solution of the woven fabric is 0.001-0.300.
The heterochromatic effect in the invention means that different colors can be seen at different angles by visually observing the front side (or the back side) of the fabric.
The nylon woven fabric is composed of cationic dyeable nylon fibers and common nylon fibers. The different dyeing characteristics of the fiber are utilized to obtain the heterochromatic effect.
Ordinary nylon fibers herein refer to conventional nylon fibers that have not been modified.
The cation dyeable nylon fiber has a sulfonic acid group content of 500-1800 ppm. When the content of the sulfonic acid group is less than 500ppm, the cationic dye is difficult to dye, even if the cationic dye is dyed, the obtained color is light, the cloth surface presents a single color of the acid dye, and the heterochromatic effect cannot be obtained; when the sulfonic acid group content is more than 1800ppm, although the dyeing effect is excellent, the yarn strength is too low to meet the requirements of clothing applications. The content of the sulfonic acid group in the present invention can be determined by the content of elemental sulfur.
The irradiation can cause the amido bond in the nylon fiber to be decomposed to generate free radicals, and the cationic dyeable nylon fiber leads in the dyeable monomer to change the stability of the polymer, thereby more easily generating a large amount of free radicals, easily reducing and decomposing part of chromophoric groups, damaging the structure and lowering the light resistance. The cationic dye septal anthraquinone compound, the isolated azo compound and the polymethine compound belong to dispersed compounds, an isolated structure exists between a chromophoric group and a dye base, and the compounds have relatively stable structures, are not easy to reduce and decompose and have good light resistance even under the illumination condition, so the compounds are preferable. In the invention, preferably, one or more of isolated anthraquinone compounds, isolated azo compounds and polymethine compounds are attached to the cation dyeable nylon fiber, and the light resistance of the nylon woven fabric can reach more than 3-4 levels.
In the invention, the difference between the absorbance peak value of the formic acid solution of the nylon woven fabric and the absorbance peak value of the strong base-formic acid solution of the nylon woven fabric is preferably 0.001-0.200. When the difference value is within the range, the cationic dye in the nylon woven fabric is not easy to be reduced by strong alkali, the stability of the dye is good, the dye is not easy to be reduced by generated free radicals during light irradiation, the decomposition reaction is not easy to occur, and the light resistance can reach more than level 4.
The nylon woven fabric can be prepared by the following production method:
firstly, uniformly mixing 1-5 g/L of leveling agent and 1-5 g/L of acid by using soft water to form an auxiliary agent solution, then simultaneously adding 0.01-5.00% of acid dye and 0.01-5.00% of cationic dye into the auxiliary agent solution, uniformly stirring to form a finishing liquid, finally putting the nylon woven fabric (the fineness of nylon fiber is 10-30 deniers) to be processed and the finishing liquid into a dyeing machine, and preserving heat for 20-60 minutes at 90-120 ℃.
The acid dyes and cationic dyes mentioned in the present invention are commercially available products, and can be synthesized according to a technique known in the art, and are not particularly limited.
And step two, uniformly mixing 1-6% of o.w.f. tannic acid color fixing agent by soft water to obtain a color fixing agent solution, putting the nylon textile dyed in the step one and the color fixing agent solution into a dyeing machine, and preserving heat for 10-40 minutes at the temperature of 60-90 ℃.
In addition, within the scope of not damaging the purpose of the invention, the finishing liquor can be used for simultaneously using assistants with other functions to carry out one-bath dyeing on the nylon fabric, and the using amount of the assistants can be adjusted according to requirements.
The present invention will be described in detail below with reference to examples and comparative examples.
The method for measuring and evaluating each index in the invention comprises the following steps:
(1) light resistance
ISO 105-B02：2014。
(2) Elemental sulfur content
According to EN 14582: the ion chromatography IC specified in the 2016 standard was analyzed.
(3) Difference in absorbance peak
Shearing 0.1g of a sample A from a woven fabric, putting the sample A into 100mL of 98% formic acid solution, and standing at normal temperature for 5min to obtain a formic acid solution 1 in which the sample A is completely dissolved;
secondly, putting the rest of the woven fabric into 2g/L sodium hydroxide solution, treating for 20min at 80 ℃, taking out and drying to obtain a sample B after strong alkali treatment. Shearing 0.1g of sample B, putting the sample B into 100mL of 98% formic acid solution, and standing at normal temperature for 5min to obtain strong base-formic acid solution 2 in which the sample B is completely dissolved;
measuring the absorbance peak values of the solution 1 and the solution 2 respectively by using an ultraviolet spectrophotometer with the model of Shimadzu UV-3150, and recording the absorbance peak values as X1 and X2 respectively, wherein the difference value between X1 and X2 is the absorbance peak value difference.
Example 1
Firstly, uniformly mixing a 2g/L leveling agent and 2g/L acid by using soft water to form an auxiliary agent solution, then simultaneously adding 1.00% o.w.f. acid dye and 1.00% o.w.f. isolated anthraquinone cationic dye (manufactured by Bixilong company) into the auxiliary agent solution, uniformly stirring to form a finishing liquid, then putting a nylon woven fabric to be processed and formed by common nylon fibers and cationic dyeable nylon fibers into a dyeing machine together with the finishing liquid, and preserving heat for 30 minutes at 98 ℃, wherein the content of sulfonic acid groups in the cationic dyeable nylon fibers is 500 ppm.
And step two, uniformly mixing the 3% o.w.f. tannic acid color fixing agent by using soft water to obtain a color fixing agent solution, putting the nylon woven fabric dyed in the step one and the color fixing agent solution into a dyeing machine, and preserving heat for 20 minutes at 80 ℃ to obtain the woven fabric.
The performance parameters of the resulting woven fabric are shown in table 1.
Example 2
The woven fabric of the present invention was obtained by replacing the woven fabric of nylon having a sulfonic acid group content of 500ppm in the cationic dyeable nylon fiber with the woven fabric of nylon having a sulfonic acid group content of 600ppm in the cationic dyeable nylon fiber in the same manner as in example 1.
The performance parameters of the resulting woven fabric are shown in table 1.
Example 3
The woven fabric of the present invention was obtained by replacing the woven fabric of nylon having a sulfonic acid group content of 500ppm in the cationic dyeable nylon fiber with the woven fabric of nylon having a sulfonic acid group content of 1200ppm in the cationic dyeable nylon fiber in the same manner as in example 1.
The performance parameters of the resulting woven fabric are shown in table 1.
Example 4
The woven fabric of nylon having a sulfonic acid group content of 500ppm in the cationic dyeable nylon fiber was replaced with a woven fabric of nylon having a sulfonic acid group content of 1800ppm in the cationic dyeable nylon fiber, and the woven fabric of the present invention was obtained in the same manner as in example 1.
The performance parameters of the resulting woven fabric are shown in table 1.
Example 5
The woven fabric of the present invention was obtained in the same manner as in example 1 except that the isolated anthraquinone cationic dye (manufactured by bisabolone corporation) was replaced with the isolated azo cationic dye (manufactured by bisabolone corporation).
The performance parameters of the resulting woven fabric are shown in table 1.
Example 6
The woven fabric of the present invention was obtained in the same manner as in example 1 except that the isolated anthraquinone cationic dye (manufactured by bisabolone corporation) was replaced with the polymethine cationic dye (manufactured by bisabolone corporation).
The performance parameters of the resulting woven fabric are shown in table 1.
Sportswear or sportswear made of the woven fabrics of examples 1-6.
Comparative example 1
The woven fabric of nylon having a sulfonic acid group content of 500ppm in the cationic dyeable nylon fiber was replaced with the woven fabric of nylon having a sulfonic acid group content of 400ppm in the cationic dyeable nylon fiber, and the woven fabric was obtained in the same manner as in example 1.
The performance parameters of the resulting woven fabric are shown in table 1.
Comparative example 2
A woven fabric was obtained in the same manner as in example 1 except that the isolated anthraquinone cationic dye (manufactured by bisabolone corporation) was replaced with a conjugated azo cationic dye (manufactured by trades).
The performance parameters of the resulting woven fabric are shown in table 1.
TABLE 1
According to the above table, the process,
(1) as is clear from examples 1 and 5, the woven fabrics obtained by dyeing with the isolated anthraquinone cationic dye have different color effects, the difference in the absorbance peak between the woven fabrics obtained by dyeing with the isolated azo cationic dye is lower than that of the woven fabrics obtained by dyeing with the isolated azo cationic dye, and the light fastness is better than that of the woven fabrics obtained by dyeing with the isolated azo cationic dye under the same conditions.
(2) As is clear from examples 1 and 6, the woven fabrics obtained by dyeing with the isolated anthraquinone-based cationic dye under the same conditions had a different color effect from those obtained by dyeing with the polymethine-based cationic dye, and the former had a slightly lower difference in absorbance peak than that of the latter, and the both had equivalent light resistance.
(3) As is clear from comparative example 1 and example 1, under the same conditions, the difference in absorbance between nylon woven fabrics having a sulfonic acid group content of 400ppm in the cationic dyeable nylon fiber is comparable to that of nylon woven fabrics having a sulfonic acid group content of 500ppm in the cationic dyeable nylon fiber, and the light resistance is comparable, but the former has no heterochromatic effect.
(4) As is clear from comparative example 2 and example 5, the woven fabrics obtained by dyeing with the conjugated anthraquinone cationic dye and the woven fabrics obtained by dyeing with the isolated azo cationic dye both have different color effects, the difference in absorbance between the former and the latter is significantly larger, and the light resistance is only 3-grade.
Claims (4)
1. A woven fabric with heterochromatic effect is characterized in that: the woven fabric is composed of cation dyeable nylon fibers and common nylon fibers, wherein the content of sulfonic acid groups in the cation dyeable nylon fibers is 500-1800 ppm; the difference between the absorbance peak value of the formic acid dissolving solution of the woven fabric and the absorbance peak value of the strong base-formic acid dissolving solution of the woven fabric is 0.001-0.300; wherein the difference between the absorbance peaks is measured by:
shearing 0.1g of sample A from a woven fabric, putting the sample A into 100mL of 98% formic acid solution, and standing for 5min at normal temperature to obtain a formic acid solution 1 in which the sample A is completely dissolved;
secondly, putting the rest of the woven fabric into 2g/L sodium hydroxide solution, treating for 20min at 80 ℃, taking out and drying to obtain a sample B subjected to strong alkali treatment, shearing 0.1g of the sample B, putting into 100mL of 98% formic acid solution, and standing for 5min at normal temperature to obtain a strong alkali-formic acid solution 2 in which the sample B is completely dissolved;
thirdly, measuring the absorbance peak values of the solution 1 and the solution 2 respectively by adopting an ultraviolet spectrophotometer with the model of Shimadzu UV-3150, and recording the absorbance peak values as X1 and X2 respectively, wherein the difference value between X1 and X2 is the difference between the absorbance peak values.
2. The woven fabric having a heterochromatic effect of claim 1, wherein: one or more of isolated anthraquinone compounds, isolated azo compounds and polymethine compounds are attached to the cation dyeable nylon fiber.
3. The woven fabric having a heterochromatic effect according to claim 1 or 2, wherein: the difference between the absorbance peak value of the formic acid dissolving solution of the woven fabric and the absorbance peak value of the strong base-formic acid dissolving solution of the woven fabric is 0.001-0.200.
4. A sportswear or sportswear made of the woven fabric having a heterochromatic effect of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811207606.7A CN111058146B (en) | 2018-10-17 | 2018-10-17 | Woven fabric with heterochromatic effect and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811207606.7A CN111058146B (en) | 2018-10-17 | 2018-10-17 | Woven fabric with heterochromatic effect and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111058146A CN111058146A (en) | 2020-04-24 |
| CN111058146B true CN111058146B (en) | 2022-06-10 |
Family
ID=70296957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811207606.7A Active CN111058146B (en) | 2018-10-17 | 2018-10-17 | Woven fabric with heterochromatic effect and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111058146B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1092047A (en) * | 1965-01-30 | 1967-11-22 | Ici Fibres Ltd | Improvements in or relating to the differential dyeing of nylon textile materials |
| JPH03193916A (en) * | 1989-12-21 | 1991-08-23 | Toray Ind Inc | Conjugate fiber dyed with cationic dye |
| JP2003183903A (en) * | 2001-12-13 | 2003-07-03 | Toray Ind Inc | Socks having grain pattern |
| CN101035848A (en) * | 2004-08-20 | 2007-09-12 | 美利肯公司 | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
| TWM456382U (en) * | 2013-02-05 | 2013-07-01 | Li Peng Entpr Co Ltd | Singly-dyed dual colors nylon fiber textile |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495660B2 (en) * | 1999-10-20 | 2002-12-17 | Honeywell International Inc | Polyamide substrate |
-
2018
- 2018-10-17 CN CN201811207606.7A patent/CN111058146B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1092047A (en) * | 1965-01-30 | 1967-11-22 | Ici Fibres Ltd | Improvements in or relating to the differential dyeing of nylon textile materials |
| JPH03193916A (en) * | 1989-12-21 | 1991-08-23 | Toray Ind Inc | Conjugate fiber dyed with cationic dye |
| JP2003183903A (en) * | 2001-12-13 | 2003-07-03 | Toray Ind Inc | Socks having grain pattern |
| CN101035848A (en) * | 2004-08-20 | 2007-09-12 | 美利肯公司 | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
| TWM456382U (en) * | 2013-02-05 | 2013-07-01 | Li Peng Entpr Co Ltd | Singly-dyed dual colors nylon fiber textile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111058146A (en) | 2020-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107916518B (en) | Process method for improving wet rubbing fastness of tatted dark cloth | |
| CA2830147A1 (en) | Method for dyeing aramid fibers and dyed aramid fibers | |
| CN110219181B (en) | National flag red dyeing process for cellulose fiber and polyester fiber blended fabric | |
| JP2007247116A (en) | Natural fiber product and dyeing method for the same | |
| CN105780254B (en) | A kind of blended inflaming retarding fabric of polyphenylene sulfide multicomponent and its dyeing | |
| CN103374776A (en) | Polyester-nylon-woven elastic fabric and producing method thereof | |
| Burkinshaw | Application of dyes | |
| TWI619773B (en) | Acid dye composition and dyeing method using same | |
| KR100535320B1 (en) | Dyeing Method for Fabrics Using Natural Dyestuffs | |
| CN111058146B (en) | Woven fabric with heterochromatic effect and application thereof | |
| Saleh et al. | Dyeing of cotton/nylon blended fabric to a solid shade in one bath | |
| CN114875554B (en) | Garment with antifouling and anti-wrinkle fabric | |
| DE3881095T2 (en) | Dyeing and printing fibers. | |
| Aitova et al. | The intensification of the processes of printing and dyeing of natural protein fiber using redox systems | |
| Bell | Recent developments in wool printing | |
| Hook et al. | The use of reactant‐fixable dyes in the dyeing of cellulosic blends | |
| JP4058690B2 (en) | Different color dyeable and knitted fabric and dyeing method thereof | |
| US3959836A (en) | Printing process | |
| CN102127314B (en) | Yellow disperse dye composition with high light fastness and application thereof | |
| CN113802394A (en) | Textile product | |
| DE2227604C2 (en) | Process for the production of denim articles | |
| KR101998289B1 (en) | Method of Eco-friendly vintage and Indigo color fiber dyeing | |
| Lee et al. | High Lightfastness Acid Dyes Synthesized from Corresponding Anthraquinone Chromophore Utilizing a Sulfonation Reaction Part 2: Dyeing Properties on Polyamide and m-Aramid Fibers and Fastness | |
| DE102015114501A1 (en) | Colored textiles based on dyed m-aramid fibers, process for their preparation and their use | |
| Lewis | Dyeing Wool Blends |
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 |