CN103588967A - Production technology for mixed type polyester resin - Google Patents
Production technology for mixed type polyester resin Download PDFInfo
- Publication number
- CN103588967A CN103588967A CN201310509108.9A CN201310509108A CN103588967A CN 103588967 A CN103588967 A CN 103588967A CN 201310509108 A CN201310509108 A CN 201310509108A CN 103588967 A CN103588967 A CN 103588967A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- cooling
- reactor
- polycondensation
- temperature
- 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.)
- Granted
Links
Abstract
The invention discloses a production technology for mixed type polyester resin. The technology comprises the following steps: sequentially performing slurry preparation, esterification, polycondensation, vacuumizing and dehydration, blocking, filtering, cooling, smashing and packaging into a warehouse on ethylene glycol, propylene glycol, trimethylolpropane, ethylene glycol acetate and p-hydroxybenzoic acid at a mole ratio of 4:3:(1-1.2):2:10, so as to obtain the mixed type polyester resin, wherein the polyester resin has the following characteristic parameters: the acid value is 70+/-2mgKOH/g, the softening point is 95-110DEG C, the viscosity is 200-300 poise (165DEG C), the curing conditions are 180DEG C/8-10min, and the mass ratio of polyester resin to epoxy resin in the finished product is 50:50. The mixed type polyester resin is mainly applicable to an indoor coating, especially a family-applied coating, so that the coating has the characteristics of being wear-resistant, anti-scratch, high in hardness and fast in curing speed, the construction efficiency of decoration workers can be improved while the practical effect of the coating can be guaranteed, and the labor cost can be saved; the production technology is simple in steps, waste pollution generated in the production processes is less, and convenient to clear, and the production technology is good in effect for large-scale batch production of factories.
Description
Technical field
The additive agent field that the present invention relates to use for the preparation of heat curable powder coating, a kind of production technique of the mixed polyester resin for indoor paint.
Background technology
Vibrin is not independent film forming generally, be mainly used in configuring polyester-amine baking varnish, PAUR paint, polyester type powder paint and unsaturated polyester varnish, in belonging to, high-grade paint, described coating film gloss is high, fullness ratio is good, weathering resistance is strong, and there is good sticking power, hardness, shock resistance, gloss retention, tint retention, the advantages such as high temperature resistance Huang, simultaneously, because the synthon of vibrin is many, choice is large, macromole formulating of recipe is theoretical ripe, can pass through acrylic resin, epoxy resin, silicone resin and fluoro-resin carry out modification, therefore, vibrin improves constantly in the status of coating industry, output is increasing, application is also expanded day by day.
The coating using in daily indoor furniture or floor; Due to indoor particular surroundings demand, the recruitment cost of the workman while simultaneously considering finishing, generally needs coating to have scratch resistant wear-resisting, the characteristic that brushing after fixing is fireballing.The diverse in function of the vibrin of mixed type, the feature capability of the vibrin after selecting different raw materials synthetic is various, at present on the market for the coating of indoor application, particularly less in scratch resistant the production method wear-resisting and vibrin that solidification effect is good, do not have systematic production technique to its centralized production.
Summary of the invention
For the problem of above-mentioned existence, the invention provides a kind of wear-resisting, the production technique of the vibrin of the fast coating of hardness high curing rate.
In order to achieve the above object, the technical solution used in the present invention is as follows: a kind of mixed polyester resin and production technique thereof, described technique is as follows: the ethylene glycol that is 4:3:1-1.2:2:10 by mol ratio, propylene glycol, trihydroxy methyl propane, acetic acid ethylene glycol and the configuration → esterification → polycondensation of P-hydroxybenzoic acid process slurry → vacuumize, dehydration → end-blocking → filtration → cooling → pulverizing → packing warehouse-in, after obtain mixed polyester resin, described vibrin characteristic parameter is as follows: acid number 70 ± 2mgKOH/g, softening temperature 95-110 ℃, viscosity 200-300 moors (165 ℃), 180 ℃/8-10min of condition of cure, in finished product, the mass ratio of vibrin and epoxy resin is 50:50.
Concrete production stage of the present invention is as follows:
Slurry configuration: be by mol ratio: the ethylene glycol of 4:3:1-1.2:2:10, propylene glycol, trihydroxy methyl propane, acetic acid ethylene glycol and P-hydroxybenzoic acid are put into and configured mixed slurry, mix and blend 1h in filler bin;
Esterification: the mixed slurry configuring is joined in reactor, and described reactor is made carrier with thermal oil, under the temperature condition of 180 ℃, the 10 ℃ of insulation reaction 1h of every rising that progressively heat up, after temperature arrives 245 ℃, insulation reaction 2-3h;
Polycondensation: after esterification completes, continue to keep reactor temperature to carry out polycondensation under the condition of 240-245 ℃, reaction 3-4h;
Vacuumize, dewater: in carrying out the process of polycondensation, reactor is vacuumized, and vacuum tightness is 40-45mmHg, and the waste gas of releasing is mainly water vapour, in waste gas, contain a small amount of reactant gas, the waste gas vacuumizing condenses into esterification waste water after circulating cooling;
End-blocking: add a small amount of trimellitic acid 1,2-anhydride to enter in reactor, make become-COOH of have-OH of polymerisate end-blocking end-blocking, temperature of reaction remains on below 200 ℃, insulation reaction 1h;
Filter: the liquid polyester resin in reactor filters through 150 object filter screens, remove impurity;
Cooling: after having filtered, to adopt the recirculated cooling water under normal temperature condition that thermal oil is cooling, reduce temperature of reaction kettle, to reach the object of cooling resin;
Pulverize: cooling solid polyester resin adopts pulverizer to be ground into powder;
Packing warehouse-in: the vibrin after pulverizing is obtained reacting finished product after packing.
In polycondensation process of the present invention, adopt Dibutyltin oxide as the catalyzer of reaction, the add-on of described Dibutyltin oxide is the 0.15%-0.2% of total amount, it is neutral that described Dibutyltin oxide is, and the process of this esterification and polycondensation and equipment are not exerted an influence, and accelerates the polycondensation process of ester class simultaneously, after reaction, catalyzer has recovery again, there is no loss, after reaction, do not need separation, do not affect the performance of vibrin.
In slurry layoutprocedure of the present invention, the molar mass of trihydroxy methyl propane and the molar mass of P-hydroxybenzoic acid are than being 1-1.2:10, during vibrin is synthetic, trihydroxy methyl propane is because the side chain degree of its molecular structure is large, movable high, thereby cause the curing speed of synthetic coating of vibrin of its production fast, facilitate decoration worker's construction, increase work efficiency, saved recruitment cost.
In polycondensation process of the present invention, adopt complex type antioxidant, described complex type antioxidant adopts 2, 6-di-tert-butylphenol is primary antioxidant, selecting trinonylphengl phosphite is secondary oxidation inhibitor, described 2, the mol ratio of 6-di-tert-butylphenol and trinonylphengl phosphite is 4:1-1.5, by two kinds of composite forming of oxidation inhibitor, in material, can learn from other's strong points to offset one's weaknesses, demonstrate synergistic effect, improve the antioxidant effect of raw material, simultaneously described in the present invention primary antioxidant and after the mixing of secondary oxidation inhibitor adds, improved the oxidation-resistance of this product, especially the resistance to acids and bases for coating has remarkable castering action, be applicable to finished product application of paints in kitchen and toilet.
The invention has the advantages that: the production technique of mixed polyester resin of the present invention, mainly to be applicable to the applicable coating of indoor particularly family, make coating there is wear-resisting scratch resistant, hardness is high and curing speed is fast feature, guaranteed in the situation of practical function of coating, improved decoration worker's operating efficiency, saved recruitment cost, this production craft step is simple simultaneously, the waste material producing in production process is of reduced contamination, easy cleaning, for large-scale produce in batches effective of factory.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
embodiment 1:the concrete preparation method of the production of a kind of mixed polyester resin of the present invention is as follows: slurry configuration: the P-hydroxybenzoic acid of the acetic acid ethylene glycol of the trihydroxy methyl propane of the propylene glycol of the ethylene glycol of 40mol, 30mol, 10mol, 20mol and 100mol is put into and in filler bin, configured mixed slurry, mix and blend 1h; In described slurry layoutprocedure, the molar mass of trihydroxy methyl propane and the molar mass of P-hydroxybenzoic acid are than being 1:10;
Esterification: the mixed slurry configuring is joined in reactor, and described reactor is made carrier with thermal oil, under the temperature condition of 180 ℃, the 10 ℃ of insulation reaction 1h of every rising that progressively heat up, after temperature arrives 245 ℃, insulation reaction 2h;
Polycondensation: after esterification completes, continue to keep reactor temperature to carry out polycondensation under the condition of 240-245 ℃, reaction 3h; In described polycondensation process, add the Dibutyltin oxide of 0.3mol as catalyzer; Add 2 of 0.4mol, the trinonylphengl phosphite of 6-di-tert-butylphenol and 0.1mol as oxidation inhibitor;
Vacuumize, dewater: in carrying out the process of polycondensation, reactor is vacuumized, vacuum tightness is 40mmHg, and the waste gas of releasing is mainly water vapour, contains a small amount of reactant gas in waste gas, and the waste gas vacuumizing condenses into esterification waste water after circulating cooling;
End-blocking: add a small amount of trimellitic acid 1,2-anhydride to enter in reactor, make become-COOH of have-OH of polymerisate end-blocking end-blocking, temperature of reaction remains on below 200 ℃, insulation reaction 1h;
Filter: the liquid polyester resin in reactor filters through 150 object filter screens, remove impurity;
Cooling: after having filtered, to adopt the recirculated cooling water under normal temperature condition that thermal oil is cooling, reduce temperature of reaction kettle, to reach the object of cooling resin;
Pulverize: cooling solid polyester resin adopts pulverizer to be ground into powder;
Packing warehouse-in: the vibrin after pulverizing is obtained reacting finished product after packing.
The characteristic parameter of the finished product vibrin obtaining is as follows: acid number 68mgKOH/g, and softening temperature 106-110 ℃, viscosity 200-220 moors (165 ℃), 180 ℃/8-10min of condition of cure, in finished product, the mass ratio of vibrin and epoxy resin is 50:50.
embodiment 2:the concrete preparation method of the production of a kind of mixed polyester resin of the present invention is as follows: slurry configuration: the P-hydroxybenzoic acid of the acetic acid ethylene glycol of the trihydroxy methyl propane of the propylene glycol of the ethylene glycol of 40mol, 30mol, 12mol, 20mol and 98mol is put into and in filler bin, configured mixed slurry, mix and blend 1h; In described slurry layoutprocedure, the molar mass of trihydroxy methyl propane and the molar mass of P-hydroxybenzoic acid are than being 1.2:10;
Esterification: the mixed slurry configuring is joined in reactor, and described reactor is made carrier with thermal oil, under the temperature condition of 180 ℃, the 10 ℃ of insulation reaction 1h of every rising that progressively heat up, after temperature arrives 245 ℃, insulation reaction 3h;
Polycondensation: after esterification completes, continue to keep reactor temperature to carry out polycondensation under the condition of 240-245 ℃, reaction 4h; In described polycondensation process, add the Dibutyltin oxide of 0.4mol as catalyzer; Add 2 of 0.4mol, the trinonylphengl phosphite of 6-di-tert-butylphenol and 0.15mol as oxidation inhibitor;
Vacuumize, dewater: in carrying out the process of polycondensation, reactor is vacuumized, vacuum tightness is 45mmHg, and the waste gas of releasing is mainly water vapour, contains a small amount of reactant gas in waste gas, and the waste gas vacuumizing condenses into esterification waste water after circulating cooling;
End-blocking: add a small amount of trimellitic acid 1,2-anhydride to enter in reactor, make become-COOH of have-OH of polymerisate end-blocking end-blocking, temperature of reaction remains on below 200 ℃, insulation reaction 1h;
Filter: the liquid polyester resin in reactor filters through 150 object filter screens, remove impurity;
Cooling: after having filtered, to adopt the recirculated cooling water under normal temperature condition that thermal oil is cooling, reduce temperature of reaction kettle, to reach the object of cooling resin;
Pulverize: cooling solid polyester resin adopts pulverizer to be ground into powder;
Packing warehouse-in: the vibrin after pulverizing is obtained reacting finished product after packing.
The characteristic parameter of the finished product vibrin obtaining is as follows: acid number 70mgKOH/g, and softening temperature 95-98 ℃, viscosity 280-300 moors (165 ℃), 180 ℃/8-10min of condition of cure, in finished product, the mass ratio of vibrin and epoxy resin is 50:50.
embodiment 3:the concrete preparation method of the production of a kind of mixed polyester resin of the present invention is as follows: slurry configuration: the P-hydroxybenzoic acid of the acetic acid ethylene glycol of the trihydroxy methyl propane of the propylene glycol of the ethylene glycol of 40mol, 30mol, 11.5mol, 20mol and 100mol is put into and in filler bin, configured mixed slurry, mix and blend 1h; In described slurry layoutprocedure, the molar mass of trihydroxy methyl propane and the molar mass of total material are than being 1.15:10;
Esterification: the mixed slurry configuring is joined in reactor, and described reactor is made carrier with thermal oil, under the temperature condition of 180 ℃, the 10 ℃ of insulation reaction 1h of every rising that progressively heat up, after temperature arrives 245 ℃, insulation reaction 2.5h;
Polycondensation: after esterification completes, continue to keep reactor temperature to carry out polycondensation under the condition of 240-245 ℃, reaction 3.5h; In described polycondensation process, the Dibutyltin oxide of heating 0.35mol is as catalyzer; 2 of 0.4mol, the trinonylphengl phosphite of 6-di-tert-butylphenol and 0.12mol as oxidation inhibitor;
Vacuumize, dewater: in carrying out the process of polycondensation, reactor is vacuumized, vacuum tightness is 43mmHg, and the waste gas of releasing is mainly water vapour, contains a small amount of reactant gas in waste gas, and the waste gas vacuumizing condenses into esterification waste water after circulating cooling;
End-blocking: add a small amount of trimellitic acid 1,2-anhydride to enter in reactor, make become-COOH of have-OH of polymerisate end-blocking end-blocking, temperature of reaction remains on below 200 ℃, insulation reaction 1h;
Filter: the liquid polyester resin in reactor filters through 150 object filter screens, remove impurity;
Cooling: after having filtered, to adopt the recirculated cooling water under normal temperature condition that thermal oil is cooling, reduce temperature of reaction kettle, to reach the object of cooling resin;
Pulverize: cooling solid polyester resin adopts pulverizer to be ground into powder;
Packing warehouse-in: the vibrin after pulverizing is obtained reacting finished product after packing.
The characteristic parameter of the finished product vibrin obtaining is as follows: acid number 72mgKOH/g, and softening temperature 100-103 ℃, viscosity 230-250 moors (165 ℃), 180 ℃/8-10min of condition of cure, in finished product, the mass ratio of vibrin and epoxy resin is 50:50.
As can be seen from the above table, its softening temperature of the vibrin of being produced by this processing method is less, and acid number is higher, viscosity is lower, causes its levelling property better, convenient brushing, and this coating its function and color under long acid soak do not change, and its hardness is higher simultaneously, scratch resistant; Its curing speed is very fast simultaneously, is better than other vibrin, therefore improves the working efficiency of finishing.
It should be noted that, above-mentioned is only preferred embodiment of the present invention, is not used for limiting protection scope of the present invention, and the equivalents of having done on the basis of above-described embodiment all belongs to protection scope of the present invention.
Claims (5)
1. the production technique of a mixed polyester resin, it is characterized in that, described technique is as follows: the ethylene glycol that is 4:3:1-1.2:2:10 by mol ratio, propylene glycol, trihydroxy methyl propane, acetic acid ethylene glycol and the configuration → esterification → polycondensation of P-hydroxybenzoic acid process slurry → vacuumize, dehydration → end-blocking → filtration → cooling → pulverizing → packing warehouse-in, after obtain mixed polyester resin, described vibrin characteristic parameter is as follows: acid number 70 ± 2mgKOH/g, softening temperature 95-110 ℃, viscosity 200-300 moors (165 ℃), 180 ℃/8-10min of condition of cure, in finished product, the mass ratio of vibrin and epoxy resin is 50:50.
2. the production technique of mixed polyester resin according to claim 1, is characterized in that, described concrete production stage is as follows:
1) slurry configuration: be by mol ratio: the ethylene glycol of 4:3:1-1.2:2:10, propylene glycol, trihydroxy methyl propane, acetic acid ethylene glycol and P-hydroxybenzoic acid are put into and configured mixed slurry, mix and blend 1h in filler bin;
2) esterification: the mixed slurry configuring is joined in reactor, and described reactor is made carrier with thermal oil, under the temperature condition of 180 ℃, the 10 ℃ of insulation reaction 1h of every rising that progressively heat up, after temperature arrives 245 ℃, insulation reaction 2-3h;
3) polycondensation: after esterification completes, continue to keep reactor temperature to carry out polycondensation under the condition of 240-245 ℃, reaction 3-4h;
4) vacuumize, dewater: in carrying out the process of polycondensation, reactor is vacuumized, and vacuum tightness is 40-45mmHg, and the waste gas of releasing is mainly water vapour, in waste gas, contain a small amount of reactant gas, the waste gas vacuumizing condenses into esterification waste water after circulating cooling;
5) end-blocking: add a small amount of trimellitic acid 1,2-anhydride to enter in reactor, make become-COOH of have-OH of polymerisate end-blocking end-blocking, temperature of reaction remains on below 200 ℃, insulation reaction 1h;
6) filter: the liquid polyester resin in reactor filters through 150 object filter screens, remove impurity;
7) cooling: after having filtered, to adopt the recirculated cooling water under normal temperature condition that thermal oil is cooling, reduce temperature of reaction kettle, to reach the object of cooling resin;
8) pulverize: cooling solid polyester resin adopts pulverizer to be ground into powder;
9) packing warehouse-in: the vibrin after pulverizing is obtained reacting finished product after packing.
3. the production technique of mixed polyester resin according to claim 2, is characterized in that, in described polycondensation process, adopts Dibutyltin oxide as the catalyzer of reaction, the 0.15%-0.2% that the add-on of described Dibutyltin oxide is total amount.
4. the production technique of mixed polyester resin according to claim 2, is characterized in that, in described slurry layoutprocedure, the molar mass of trihydroxy methyl propane and the molar mass of P-hydroxybenzoic acid are than being 1-1.2:10.
5. the production technique of mixed polyester resin according to claim 2, it is characterized in that, in described polycondensation process, adopt complex type antioxidant, described complex type antioxidant adopts 2,6-di-tert-butylphenol is primary antioxidant, selecting trinonylphengl phosphite is secondary oxidation inhibitor, described 2, and the mol ratio of 6-di-tert-butylphenol and trinonylphengl phosphite is 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310509108.9A CN103588967B (en) | 2013-10-25 | 2013-10-25 | A kind of production technique of mixed polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310509108.9A CN103588967B (en) | 2013-10-25 | 2013-10-25 | A kind of production technique of mixed polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103588967A true CN103588967A (en) | 2014-02-19 |
| CN103588967B CN103588967B (en) | 2016-01-20 |
Family
ID=50079307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310509108.9A Active CN103588967B (en) | 2013-10-25 | 2013-10-25 | A kind of production technique of mixed polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103588967B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4067452A4 (en) * | 2019-11-29 | 2023-12-06 | Kukdo Chemical Co., Ltd. | Method for manufacturing ultra-low-temperature, fast-curable epoxy resin, and powder coating composition comprising resin manufactured thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425048A (en) * | 2000-03-24 | 2003-06-18 | 国际壳牌研究有限公司 | Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol |
| CN101445591A (en) * | 2008-12-26 | 2009-06-03 | 广州擎天实业有限公司 | Polyester resin with high acid value and low acid value for environment-friendly dry blended low-gloss powder coating and preparation method thereof |
| CN103172992A (en) * | 2011-12-21 | 2013-06-26 | 常州市华润复合材料有限公司 | Matrix resin for highly waterproof gel coat and preparation method thereof |
-
2013
- 2013-10-25 CN CN201310509108.9A patent/CN103588967B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425048A (en) * | 2000-03-24 | 2003-06-18 | 国际壳牌研究有限公司 | Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol |
| CN101445591A (en) * | 2008-12-26 | 2009-06-03 | 广州擎天实业有限公司 | Polyester resin with high acid value and low acid value for environment-friendly dry blended low-gloss powder coating and preparation method thereof |
| CN103172992A (en) * | 2011-12-21 | 2013-06-26 | 常州市华润复合材料有限公司 | Matrix resin for highly waterproof gel coat and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4067452A4 (en) * | 2019-11-29 | 2023-12-06 | Kukdo Chemical Co., Ltd. | Method for manufacturing ultra-low-temperature, fast-curable epoxy resin, and powder coating composition comprising resin manufactured thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103588967B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102838819B (en) | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) | |
| CN102181000A (en) | Water-emulsion-type high-efficiency terminator for polyvinyl chloride and preparation method thereof | |
| CN103554453B (en) | A kind of industrial machinery coating vibrin and production technique thereof | |
| CN103613850B (en) | A kind of Filament for vermin-proof plastic woven bag | |
| CN105001027A (en) | Fluorne compound preparing method | |
| CN105482218A (en) | Production process of composite heat stabilizer with zinc calcium cyanurate as matrix | |
| CN106432703A (en) | Hydroxyl polyester resin with high solid content and preparation method and application thereof | |
| CN103588967B (en) | A kind of production technique of mixed polyester resin | |
| CN104497282B (en) | A kind of polyester hot-melt adhesive used for powder coating and preparation method thereof | |
| CN110606960A (en) | Preparation method of rectangular strip-shaped Al-MOF material | |
| CN104557446B (en) | A kind of method preparing vinylidene fluoride monomers | |
| CN104030886B (en) | Be the method that 2,2-difluoroethanol prepared by raw material with the fluoro-1-halothane of 2,2-bis- | |
| CN104592504A (en) | Method for preparing light stabilizer 622 | |
| CN101967252B (en) | Calcium magnesium zinc composite thermal stabilizer, preparation method and application thereof | |
| CN102336897B (en) | Alkyd resin for quickly drying alkyd enamel paint and preparation method thereof | |
| CN104356376A (en) | Method for improving monoester content in nonyl phenol polyoxyethylene ether phosphate | |
| CN103554451B (en) | A kind of anti-solarization water resistant polyester resin and production technique thereof | |
| CN103554454A (en) | Outdoor type polyester resin and production process thereof | |
| CN104479115A (en) | Method for preparing linear polyester resin | |
| CN104710613B (en) | A kind of solvothermal preparation method of semiaromatic polyamide composition | |
| CN103789836A (en) | Preparation method for magnesium hydroxide crystal whiskers | |
| CN106753809B (en) | Preparation method for synthesizing high-molecular-weight multi-branched citrate ester derivative by using vegetable oil ester and citrate ester | |
| CN103666137A (en) | Preparation method of wall coating | |
| CN103694463A (en) | Preparation method of soya alkyd resin | |
| CN103628177A (en) | Flame-retardant filaments for plastic woven bag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |