CN114057948B - Water-based acrylic acid modified resin and preparation method thereof - Google Patents
Water-based acrylic acid modified resin and preparation method thereof Download PDFInfo
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- CN114057948B CN114057948B CN202111346921.XA CN202111346921A CN114057948B CN 114057948 B CN114057948 B CN 114057948B CN 202111346921 A CN202111346921 A CN 202111346921A CN 114057948 B CN114057948 B CN 114057948B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a water-based acrylic acid modified resin and a preparation method thereof, wherein the water-based acrylic acid modified resin is prepared from a hard monomer: 10-30 parts; soft monomer: 20-50 parts; functional monomer: 10-30 parts; emulsifying agent: 6-40 parts; organosilicon monomer: 20-50 parts; polymerization regulator: 0.1-5 parts; and (3) an initiator: 1-10 parts; neutralizing agent: 2-10 parts; deionized water: 135-600 parts. The preparation method has short time, low reaction temperature and simple reaction process; the obtained water-based acrylic resin has the advantages of low viscosity, good stability, high brightness, high fullness, good film forming, certain toughness, good smoothness of the paint film after being coated and dried, and good stripping property after being coated on a PET film.
Description
Technical Field
The invention relates to a water-based acrylic acid modified resin and a preparation method thereof, in particular to a polyurethane emulsion with larger molecular weight polymerized by a special process, so that the viscosity of a film forming adhesive is stronger, the film forming hardness is improved on the premise of ensuring the viscosity, the film forming brightness is improved, the film forming is soft and has certain toughness, and the water-based acrylic acid modified resin is suitable for the bright back adhesive industry.
Background
Compared with the traditional solvent-based paint, the water-based paint has the advantages of low price, safe use, resource and energy conservation, environmental pollution reduction, public nuisance reduction and the like, and the research of the water-based polyurethane adhesive is rapidly developed along with the enhancement of the safety and environmental awareness of people. The aqueous polyurethane adhesive is an adhesive formed by dissolving polyurethane in water or dispersing the polyurethane in the water, and has the advantages of no solvent, no pollution, good film forming property, strong adhesive force, easy blending of other polymers, particularly emulsion polymers, and the like, which are beneficial to modification. And thus has become the primary direction of current development of the coatings industry. The water-based polyurethane resin is increasingly important today when the country advocates energy conservation and environmental protection.
The aqueous polyurethane resin uses water instead of an organic solvent as a diluent, has nonflammable fire resistance, effectively reduces fire occurrence, has extremely high adhesive force with a substrate, and has higher surface glossiness. The aqueous polyurethane resin has the advantages of better environmental protection, no toxicity, no inflammability and no explosion, and is extremely safe in storage and transportation. The water is used as a medium, the water-based ink is nontoxic and incombustible, pollution-free, free of danger, small in smell, free of environmental pollution, energy-saving, high in viscosity, good in flexibility and strong in adhesion to various paper, is suitable for a substrate which is easy to erode by an organic solvent, can be mixed with various aqueous resins, is beneficial to improving performance and reducing cost, is suitable for dye ink, is an ideal product for promoting advertising and exhibition, is bright in printing effect color and good in ink absorbency, and is loved by customers.
Disclosure of Invention
The invention aims to overcome the defect that water-based polyurethane is easy to return to viscosity at normal temperature in the prior art, and provides a water-based acrylic modified resin which can be stably stored at normal temperature and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the aqueous acrylic modified resin is prepared from the following raw materials in parts by mass:
hard monomer: 10-30 parts;
soft monomer: 20-50 parts;
functional monomer: 10-30 parts;
emulsifying agent: 6-40 parts;
organosilicon monomer: 20-50 parts;
polymerization regulator: 0.1-5 parts;
and (3) an initiator: 1-10 parts;
neutralizing agent: 2-10 parts;
deionized water: 135-600 parts.
Preferably, the emulsifier is one or more than two of sodium dodecyl sulfate, alkylphenol ethoxylates, sodium dodecyl sulfonate, octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether ammonium sulfate;
preferably, the hard monomer is at least one of methyl methacrylate, methyl acrylate, vinyl acetate, ethyl methacrylate, methyl tert-butyl acrylate, acrylonitrile and styrene;
preferably, the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate
Preferably, the functional monomer is at least one of hydroxyethyl methacrylate, hydroxypropyl acrylate, methacrylic acid, acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylic acid, butyl acrylate, 2-ethylhexyl acrylate and hydroxypropyl acrylate;
preferably, the organic silicon monomer is at least one of methyl chlorosilane, phenyl chlorosilane, methyl vinyl chlorosilane, propyl trichlorosilane and vinyl siloxane;
preferably, the neutralizing agent is one or more than two of ammonia water, monoethanolamine, diethanolamine and triethanolamine;
preferably, the polymerization regulator: n-dodecyl mercaptan.
The emulsifier is alkylphenol polyoxyethylene ether; the hard monomer is methyl methacrylate and acrylonitrile; the soft monomer is butyl acrylate; the initiator is ammonium persulfate; the functional monomer is hydroxypropyl acrylate; neutralizing agent: ammonia water; polymerization regulator: n-dodecyl mercaptan.
The preparation method of the aqueous acrylic emulsion comprises the following steps:
1) 2-10 parts of emulsifier is dissolved in 50-300 parts of water to obtain an emulsifier aqueous solution;
2) Uniformly mixing 1-10 parts of emulsifying agent and 10-50 parts of water, and then adding 20-50 parts of organosilicon monomer and 0.1-5 parts of polymerization regulator, uniformly mixing to obtain emulsified organosilicon monomer A;
3) Uniformly mixing 1-10 parts of emulsifying agent and 20-100 parts of water, and then adding 10-30 parts of hard monomer, 20-50 parts of soft monomer and 10-30 parts of functional monomer, uniformly mixing to obtain emulsified monomer B;
4) 1-10 parts of initiator is dissolved in 5-50 parts of deionized water to obtain an initiator aqueous solution.
5) Mixing 2-10 parts of emulsifying agent and 50-100 parts of water uniformly, heating to 70-85 ℃, then starting to dropwise add the emulsified organic silicon monomer A and 3-5 parts of initiator aqueous solution simultaneously by using a peristaltic pump for 2 hours, and reacting for 2 hours at constant temperature after the dropwise addition is finished. Then, a peristaltic pump is used for simultaneously dripping the emulsified monomer B and 5-10 parts of initiator aqueous solution for 2 hours, the constant temperature reaction is carried out for 2 hours after the dripping, the temperature is reduced after the reaction is finished, 2-10 parts of neutralizer is added for regulating the pH value to 7-8, and a 200-mesh filter screen is used for filtering, thus obtaining the aqueous acrylic acid modified resin.
Preferably, the dripping rate of the emulsified silicone monomer A in step 5) is 0.1 to 1 part/min. The dropping rate of the emulsion monomer B is 0.2 to 1.5 parts/min.
The beneficial effects achieved by the invention are as follows:
the reaction process is simple; the aqueous acrylic resin obtained by the invention has the advantages of low viscosity, good stability, high brightness, high fullness, good film forming, certain toughness, good smoothness of the paint film after being coated and dried, and good peelability after being coated on a PET film.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1
1) 2g of sodium dodecyl sulfate and 72g of water are stirred and mixed uniformly to obtain an aqueous solution of sodium dodecyl sulfate;
2) Adding 1g of alkylphenol ethoxylate into 30g of water, stirring at 500rpm for 2min, adding 35g of vinyl siloxane, 0.2g of n-dodecyl mercaptan and stirring at 800rpm for 15min to obtain an emulsified organosilicon monomer A;
3) Adding 2g of alkylphenol ethoxylates into 40g of water, stirring at 500rpm for 2min, adding 10g of methyl methacrylate, 40g of butyl acrylate, 15g of hydroxypropyl acrylate and 8g of acrylonitrile, and stirring at 800rpm for 15min to obtain an emulsified monomer B;
4) 1.3g of ammonium persulfate is added into 8g of deionized water, and the mixture is uniformly mixed and dissolved to obtain an ammonium persulfate aqueous solution.
5) 2g of sodium dodecyl sulfate and 72g of water are stirred and mixed uniformly, the temperature is raised to 80 ℃, then a peristaltic pump is used for starting to simultaneously dropwise add the emulsified organic silicon monomer A and 3.5g of initiator aqueous solution for 2 hours, and the constant temperature reaction is carried out for 2 hours after the dropwise addition is completed. Then, a peristaltic pump is used for beginning to simultaneously dropwise add the emulsion monomer B and 5.6g of initiator aqueous solution, the dropwise adding time is 2 hours, the constant temperature reaction is carried out for 2 hours after the dropwise adding is finished, the temperature is reduced after the reaction is finished, 3g of neutralizer is added for regulating the pH value to 7-8, and a 200-mesh filter screen is used for filtering, so that the aqueous acrylic acid modified resin sample 1 is obtained. The dropping rate of the emulsified silicone monomer A was 0.55g/min. The dripping rate of the emulsion monomer B is 0.96g/min
Example 2
1) 2g of sodium dodecyl sulfate and 72g of water are stirred and mixed uniformly to obtain an aqueous solution of sodium dodecyl sulfate;
2) Adding 1g of alkylphenol ethoxylate into 30g of water, stirring at 500rpm for 2min, adding 45g of vinyl siloxane, 0.2g of n-dodecyl mercaptan and stirring at 800rpm for 15min to obtain an emulsified organosilicon monomer A;
3) Adding 2g of alkylphenol ethoxylates into 40g of water, stirring at 500rpm for 2min, and adding 5g of methyl methacrylate, 35g of butyl acrylate, 15g of hydroxypropyl acrylate and 8g of acrylonitrile, and stirring at 800rpm for 15min to obtain an emulsified monomer B;
4) 1.3g of ammonium persulfate is added into 8g of deionized water, and the mixture is uniformly mixed and dissolved to obtain an ammonium persulfate aqueous solution.
5) 2g of sodium dodecyl sulfate and 72g of water are stirred and mixed uniformly, the temperature is raised to 80 ℃, then a peristaltic pump is used for starting to simultaneously dropwise add the emulsified organic silicon monomer A and 3.5g of initiator aqueous solution for 2 hours, and the constant temperature reaction is carried out for 2 hours after the dropwise addition is completed. Then, a peristaltic pump is used for starting to simultaneously dropwise add the emulsion monomer B and 5.6g of initiator aqueous solution for 2 hours, the constant temperature reaction is carried out for 2 hours after the dropwise addition, the temperature is reduced after the reaction is finished, 3g of neutralizer is added for regulating the pH value to 7-8, and a 200-mesh filter screen is used for filtering, so that the aqueous acrylic acid modified resin sample 2 is obtained. The dropping rate of the emulsified silicone monomer A was 0.55g/min. The dripping rate of the emulsion monomer B is 0.96g/min
Example 3
1) 2g of sodium dodecyl sulfate and 72g of water are stirred and mixed uniformly to obtain an aqueous solution of sodium dodecyl sulfate;
2) Adding 1g of alkylphenol ethoxylate into 30g of water, stirring at 500rpm for 2min, adding 25g of vinyl siloxane, 0.2g of n-dodecyl mercaptan and stirring at 800rpm for 15min to obtain an emulsified organosilicon monomer A;
3) Adding 2g of alkylphenol ethoxylates into 40g of water, stirring at 500rpm for 2min, adding 15g of methyl methacrylate, 45g of butyl acrylate, 15g of hydroxypropyl acrylate and 8g of acrylonitrile, and stirring at 800rpm for 15min to obtain an emulsified monomer B;
4) Adding 1.3g of ammonium persulfate into 8g of deionized water, and uniformly mixing and dissolving to obtain an ammonium persulfate aqueous solution;
5) Stirring and mixing 2g of sodium dodecyl sulfate and 72g of water uniformly, heating to 80 ℃, then starting to dropwise add the emulsified organic silicon monomer A and 3.5g of initiator aqueous solution simultaneously by using a peristaltic pump for 2 hours, and reacting for 2 hours at constant temperature after the dropwise addition is finished; then, simultaneously dripping the emulsified monomer B and 5.6g of initiator aqueous solution by using a peristaltic pump for 2 hours, reacting for 2 hours at constant temperature after dripping, cooling after finishing the reaction, adding 3g of neutralizer to adjust the pH value to 7-8, and filtering by using a 200-mesh filter screen to obtain a water-based acrylic acid modified resin sample 3; the dropping rate of the emulsified silicone monomer A was 0.55g/min. The dripping rate of the emulsion monomer B is 0.96g/min
The aqueous acrylic resin detection technique parameters prepared in examples 1 to 3 above were used according to the following procedure:
1) Appearance inspection (visual inspection)
The emulsion sample was poured into a cuvette and the color, shape, transparency, etc. of the emulsion was visually observed under sufficient natural light conditions.
2) Viscosity test (NDJ-1 rotary viscometer)
The viscosity was measured with an NDJ-1 rotational viscometer.
3) Solid content detection (baking oven method)
Weighing the mass M1 of the tinfoil cup; heating the oven to 130 ℃, weighing the mass M of the sample in a small tin paper cup, and carefully placing the sample in a constant-temperature oven; after baking for 1 hour, the sample was taken out and put into a dryer, cooled to room temperature, and then weighed as mass M2.
The solid content is calculated according to the following formula: x= (M2-M1)/mx100%.
4) PH value detection
General method for measuring PH value in GB/T23769-2009 aqueous solution
5) Scratch gloss detection (gloss instrument 60 degree)
The emulsion was scraped on a PET film with a 1#RK wire rod, baked in an oven at 130℃for 30s, dried and taken out, and the gloss of the paint film was measured using a gloss meter.
6) Compatibility with aqueous dyes (pigments) and scratch detection (visual inspection)
The aqueous dye color ink and the aqueous pigment color ink with the same proportion are respectively added under low-speed stirring, and the incompatibility conditions such as flocculation, precipitation, layering and the like are observed.
7) Scratch resistance and abrasion resistance test of paint film (ink printing decoloration tester test)
Scraping the emulsion on aluminum foil by using a 1#RK wire rod, baking the emulsion in a baking oven at 130 ℃ for 30 seconds, taking the emulsion out, and testing the emulsion by using an ink printing decoloration tester, wherein the pressure is 4 pounds, the speed is 43 times/minute, and the friction times are 30 times; the wear of the coating was observed.
8) Paint film adhesion detection of PET film aluminum plating surface and PET film surface (3M adhesive tape test method)
Scraping the aluminum plating surface and the film surface of the PET aluminizer by using a 1#RK wire rod, baking for 30s at 130 ℃ in an oven, drying, taking out, placing on a smooth and clean glass test bed, sticking a 3M transparent adhesive tape with the thickness of 18mm on a paint film, and pressing by using a thumb; after being placed for 30 seconds, the adhesive tape is pulled up rapidly by force; judging whether the adhesive force is good or not according to the falling-off condition of the paint film. The decision level is as follows:
the pull-off is not carried out by A, the pull-off is less than 1/3 of that of B, the pull-off is 1/3-1/2 of that of C, the pull-off is 1/2-2/3 of that of D, the pull-off is 2/3-complete, and the pull-off is completely easy to be carried out by F;
finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. An aqueous acrylic modified resin, characterized in that: the preparation method comprises the following steps:
1) 2g of sodium dodecyl sulfate and 72g of water are stirred and mixed uniformly to obtain an aqueous solution of sodium dodecyl sulfate;
2) Adding 1g of alkylphenol ethoxylate into 30g of water, stirring at 500rpm for 2min, adding 35g of vinyl siloxane, 0.2g of n-dodecyl mercaptan and stirring at 800rpm for 15min to obtain an emulsified organosilicon monomer A;
3) Adding 2g of alkylphenol ethoxylates into 40g of water, stirring at 500rpm for 2min, adding 10g of methyl methacrylate, 40g of butyl acrylate, 15g of hydroxypropyl acrylate and 8g of acrylonitrile, and stirring at 800rpm for 15min to obtain an emulsified monomer B;
4) Adding 1.3g of ammonium persulfate into 8g of deionized water, and uniformly mixing and dissolving to obtain an ammonium persulfate aqueous solution;
5) Stirring and mixing 2g of sodium dodecyl sulfate and 72g of water uniformly, heating to 80 ℃, then starting to dropwise add the emulsified organic silicon monomer A and 3.5g of initiator aqueous solution simultaneously by using a peristaltic pump for 2 hours, and reacting for 2 hours at constant temperature after the dropwise addition is finished; then, simultaneously dripping the emulsified monomer B and 5.6g of initiator aqueous solution by using a peristaltic pump for 2 hours, and reacting for 2 hours at constant temperature after dripping; cooling after the reaction is finished, adding 3g of neutralizer to adjust the pH value to 7-8, and filtering by a 200-mesh filter screen to obtain the catalyst.
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| CN102532401B (en) * | 2011-12-23 | 2014-01-08 | 上海奇想青晨新材料科技股份有限公司 | Elastic emulation and preparation method thereof |
| CN102827320A (en) * | 2012-09-17 | 2012-12-19 | 上海富臣化工有限公司 | Styrene acrylic emulsion for interior wall coating material, and preparation method thereof |
| CN104356980A (en) * | 2014-10-31 | 2015-02-18 | 中科院广州化学有限公司 | Organic silicon modified styrene-acrylic emulsion type pressure sensitive glue with high steric hindrance and low residual, and preparation method and application thereof |
| CN104342073A (en) * | 2014-10-31 | 2015-02-11 | 中科院广州化学有限公司 | Organic silicon modified phenyl emulsion pressure-sensitive adhesive with high release force and low residue as well as preparation method thereof and application |
| CN105907343A (en) * | 2016-05-17 | 2016-08-31 | 湖南省和祥润新材料有限公司 | Water-borne acrylic compound adhesive and preparing method thereof |
| JP2021138942A (en) * | 2020-03-06 | 2021-09-16 | 日信化学工業株式会社 | Emulsion composition, coating agent and laminate |
| CN112662347A (en) * | 2020-12-23 | 2021-04-16 | 湖南省和祥润新材料有限公司 | Water-based acrylic acid composite adhesive and preparation method thereof |
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