CN1031833C - Resin binder for refractory materials and preparing process thereof - Google Patents
Resin binder for refractory materials and preparing process thereof Download PDFInfo
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- CN1031833C CN1031833C CN 91100841 CN91100841A CN1031833C CN 1031833 C CN1031833 C CN 1031833C CN 91100841 CN91100841 CN 91100841 CN 91100841 A CN91100841 A CN 91100841A CN 1031833 C CN1031833 C CN 1031833C
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Abstract
The present invention relates to a resin binder for producing refractory lining materials and a preparing process thereof. The preparing process comprises: mixing linear phenolic resin with furan resin according to a weight ratio of 20 to 70: 80 to 30; adding a high boiling solvent of which the weight is 0.1 to 1.5 timers greater than that of the linear phenolic resin, and 0.01 to 1% of additives; carrying out copolycondensation for 0.5 to 4 hours at 120 to 165 DEG C and 0.03 to 0.1MPa, and regulating viscosity to 10 to 200 poises with diluents. The product of the present invention can be used for producing magnesium calcium carbon bricks, which is favorable for producing the refractory materials with good quality and low cost by using calcium contained raw materials widely distributed. The product can also be used for producing magnesium carbon bricks.
Description
The present invention relates to produce resinoid bond that fire proof material of furnace lining, particularly calcic refractory brick uses and preparation method thereof.
Along with smelting condition to high-temperature oxygen-enriched development, the present MgO-C brick that generally adopts is aggravated by carbon reduction at smelting temperature during greater than 1700 ℃, magnesium oxide, oxygen-rich smelting makes the oxidation of coal aggravation again, causes the furnace lining material rate of decay fast.The celebrity of Japanese fire resisting material circle cross the limit bright, become that people's such as Lai Yongyi, big Shiquan studies show that the MgO-CaO-C brick is better than MgO-C brick solidity to corrosion, wastage rate are low.People such as U.S. J.W.Stendera studies show that, in various oxide refractories commonly used, it is the most stable and desulfuration efficiency is high to contain the calcium oxide basic refractory.But owing to contain the easy aquation of material of calcium oxide, the wedding agent of selecting to be suitable for is to develop the calcic refractory materials difficult problem of fine solution not as yet both at home and abroad always.
Still generally adopt with pitch at present and make wedding agent, the calcic refractory materials is produced in hot method moulding.This method before batch mixing, raw material and wedding agent need be heated to 500 ℃ and 200 ℃ respectively, operation inconvenience, energy consumption is big, and because pitch is fuming contaminate environment, the health that working condition is abominable, influence operator.
Adopt resol to prepare magnesia-calcium-carbon brick, exist calcium oxide aquation problem, cause volumetric expansion, make brick be full of cracks efflorescence as the wedding agent formed at normal temp, can not be practical.Possible cause has: 1. during phenol formaldehyde condensation, because the wetting ability of phenolic hydroxyl group, it is very difficult the water content in the resin being reduced to below 5/1000ths, and the free-water that exists in this resin is the immediate cause of CaO aquation; 2. in the resin-CH OH base can dehydration in solidification process and make the CaO aquation; 3. the low-molecular weight polymer that produces in remaining phenol in the resin or the reaction process also can react with CaO, causes volumetric expansion, causes the be full of cracks or the efflorescence of brick.
Through investigation and the CA of international online retrieval 1967-1990 and the patent of 1963-1990, develop resin at present in the world as anhydrous binder, be that modification is carried out on the basis all with phenol vinegar, by reactions such as resol and micromolecular compound such as Texacar PCs, to eliminate the factor of phenolic hydroxyl group and CaO reaction.Introduced in the presence of salt of wormwood as the Japan clear 60-26065 of special permission communique, made the reaction of resol and Texacar PC make viscous liquid; The clear 61-2627 of special permission communique has introduced with the linear phenol vinegar of ethylene oxide treatment resin; The flat 1-40788 of special permission communique has introduced with epoxy chloropropane and has handled linear phenolic resin.
With regard to China's present circumstances, industrial chemicals deficiencies such as ethylene carbonate or inferior propyl ester, price is more expensive, and it is higher to adopt aforesaid method to produce the anhydrous binder cost.In addition, brickmaking main raw material magnesite resource is undesirable at China's distributed pole, is only provided by northeast Liao Haidiqu, causes transportation inconvenience, the price height.That China has is abundant, grade is high contains the CaO raw material, and as konite, rhombspar, Wingdale, it is wide to distribute, and draws materials easily.But also there is not a kind of resin can be so far as pure calcium magnesia sand, graphite; Or the wedding agent of electric smelting rhombspar, Wingdale (consumption is greater than 20%), electrosmelted magnesite clinker, graphite.
The purpose of this invention is to provide a kind of domestic raw material, cost is low, performance is good resinoid bond and preparation method thereof of being based on, cause a cracking atomizing difficult problem to solve the system mg-ca-carbon refractory because of the CaO aquation, produce the calcic refractory materials thereby make full use of the widely distributed CaO resource of China.
The objective of the invention is to realize in the following way:
With linear phenolic resin and viscosity is that the furane resin that 5-500 moors mix by the weight ratio of 20-70: 80-30, add the high boiling solvent of 0.5-1.5 times of linear phenolic resin weight and the additive of 0.01-1%, under 120-165 ℃ of temperature and 0.03-0.1MPa vacuum tightness copolycondensation 0.5-4 hour, add thinner again viscosity is transferred to the 10-200 pool, obtain the viscous liquid of brown or black, be final resin wedding agent of the present invention.
The molecular weight of above-mentioned linear phenolic resin is 500-1500, and water content is less than 1% weight (all being weight percentage with the % that hereinafter occurs);
Described furane resin can be furfuryl alcohol resin or furfuryl resin;
Described high boiling solvent can be washing oil, carbolineum, ethylene carbonate, Texacar PC or phthalic acid ester class, is selected from rutgers, diethyl phthalate, phthalic acid dibutyl ester and dioctyl phthalate;
Described additive can be Phenylsulfonic acid, right-toluene sulfonic acide, methylsulphonic acid, sulfuric acid, phosphoric acid, aluminum chloride or zinc chloride.
Described thinner can be an aromatic solvent, is selected from toluene, dimethylbenzene, trimethylbenzene, washing oil, carbolineum; Or carbonates, be selected from methylcarbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, Texacar PC; Or acetates, be selected from ritalin, vinyl acetic monomer, propyl acetate, N-BUTYL ACETATE, amyl acetate-n, capryl acetate, octyl acetate; Or the phthalic acid ester class, be selected from rutgers, diethyl phthalate, phthalic acid dibutyl ester and dioctyl phthalate.
Above-mentioned linear phenolic resin can use the commercially available prod, also can adopt following method to prepare:
With formaldehyde and phenol with 0.5-1: 1 mixed in molar ratio, the acid that adds phenol weight 0.1-0.8% be as catalyzer, heating, back flow reaction 0.5-4 hour, under normal pressure, the back was under 0.01-0.1MPa vacuum tightness earlier, distilled 1-4 hour, to generate linear phenolic resin and to remove water in the system; Add high boiling solvent again, under 0.05-0.1MPa vacuum tightness, heating makes temperature of reaction be elevated to 140-165 ℃ gradually, so that phenol formaldehyde condensation carries out relatively fully and reduces the content of remaining phenol in the resin.
Described acid as catalyzer can be hydrochloric acid, sulfuric acid, oxalic acid or phosphoric acid.
Described high boiling solvent as hereinbefore.
The inventive method has following advantage:
1. the raw material of Shi Yonging is based on domesticly, and the source is abundant, and cheap, production cost is low.
2. utilize not that crosslinked copolycondensation takes place for the furane resin and the resol of hydroxyl, can reduce the relative content of phenolic hydroxyl group on the one hand, stop phenolic hydroxyl group and CaO effect by polymer effect simultaneously, the possibility of minimizing CaO aquation.
3. furane resin have higher carbon residue behind high temperature, can improve the intensity of refractory materials.
4. in preparation resol process, add high boiling solvent, the heat of polymerization of reaction is distributed preferably, and phenol formaldehyde condensation is more complete, can reduce the content of remaining phenol in the resin, improve the molecular weight of resol.
5. add an amount of thinner, make reaction system have suitable viscosity, mixing homogeneous has guaranteed the quality of product.
Final resin wedding agent of the present invention is brown or the black viscous liquid, water content≤0.4%, carbon residue 〉=45%, low volatilization component (35 ℃, 1 hour)≤2%, free phenol≤1%, solid content 〉=75%.
Above-mentioned water content is pressed the GB-2288-80 method and is measured, and carbon residue is pressed the GB-268-77 method and measured, and free phenol is pressed the HG5-1342-80 method and measured, and other indexs are all measured according to a conventional method.
Final resin wedding agent of the present invention can be used as the wedding agent of producing magnesia-calcium-carbon brick, also can be used as the wedding agent of magnesia carbon brick.
Will be thick, in, fine grain electrosmelted magnesite clinker, burnt dolomite or sintering calcium magnesia sand, the listed weight proportion batching of graphite according to the form below, coarse particles electrosmelted magnesite clinker and electric smelting rhombspar or burnt dolomite or electric smelting calcium magnesia sand or sintering calcium magnesia sand in adding successively, add about 5% resinoid bond of the present invention again, after mixing, add graphite and electrosmelted magnesite clinker fine powder again, behind the mixing, on pressing machine, be pressed into the cylinder shape sample of diameter 43.6cm by Standard Module, after 350 ℃ of thermal treatment, it is listed to test its performance such as following table: (table is seen the literary composition back) is under condition situation about the same, magnesia-calcium-carbon brick or magnesia-calcium brick with final resin wedding agent preparation of the present invention, its over-all properties is better than or is equivalent to the performance level announced in the Japan special permission communique, and cost is than being low.Use the magnesia-calcium-carbon brick of commercially available BT-2 wedding agent preparation that crackle is arranged, can't measure its performance.With the MgO-CaO-C brick that product of the present invention is made as wedding agent, every performance index have all surpassed the MgO-CaO-C brick of making wedding agent with pitch.
Respectively at LD combined blown converter and H, it is on probation to carry out industry on the F external refining stove, has all obtained the effect of being satisfied with the MgO-CaO-C brick of resinoid bond of the present invention trial production and MgO-C brick.In the industry of LD combined blown converter is on probation, adopt harsh smelting condition, etch rate with the MgO-CaO-C brick of resin-bonded of the present invention preparation is the 0.38mm/ stove, and the tackling key problem index of now deciding high-quality MgO-C brick is etch rate≤0.5mm/ stove, and as seen the fire proof material of furnace lining that makes with this product wedding agent has surpassed the tackling key problem high-quality index.In LF external refining furnaceman was already on probation, the MgO-CaO-C brick for preparing with resinoid bond of the present invention can reach 3-8 times of original use magnesia chrome brick work-ing life.According to Shanxi Steelworks's estimation, original annual need of LF stove with 600 tons of magnesia chrome bricks, the MaO-CaO-C brick and the molten bath brick of the preparation of current series product wedding agent are supporting, and only 75 tons just can meet the demands.4800 yuan/ton of magnesia chrome brick prices, the MaO-CaO-C brick is by 4000 yuan of/ton calculating, only the cost of anti-material that stove year reduces furnace bottom, slag line brick can reach 2,580,000 yuan, the energy consumption of saving if will replace high temperature to burn till magnesia chrome brick, reduce the efficient that the stove turnover time improved and improved the steel alloy quality, reduced factors such as labor strength and taken into account, not only economic benefit is very remarkable, and social benefit also is appreciable.
Aboundresources such as China's rhombspar, Wingdale, it is wide, of high grade to distribute.If use the MgO-CaO-C brick, or MgO-C brick integrated block heater, can solve China and too concentrate the difficult contradiction of other area use because of the magnesia place of production, will minimize transport costs greatly, alleviate the transportation difficulty, the cost of reduction refractory materials.
Adopt final resin wedding agent formed at normal temp method of the present invention to compare with adopting the hot method method of forming production of pitch wedding agent refractory materials, save energy not only, easy to use, quality of item, performance improve greatly, and prevented environmental pollution, improve labor condition, helped ensureing operator's health.
Resinoid bond of the present invention provides a kind of excellent property cheap anhydrous binder for production high-quality MgO-CaO-C and MgO-C refractory materials, filled up domestic blank, simultaneously also provide a new kind and new production method for resin binder for refractory materials in the world.
Following examples specify the process for preparing resinoid bond with the inventive method:
Embodiment 1:
With 100 gram phenol, 65 milliliters of weight concentrations are that 35% formaldehyde and the 2 gram oxalic acid capacity of being added to are in the there-necked flask of 1000ml, are heated to backflow, keep this thermotonus after 1.5 hours, distill out the water about 100 milliliters under normal pressure.Add 50 gram washing oil, under 0.05MPa vacuum tightness, continue water is steamed.Along with steaming of water, reacting liquid temperature rises to 155 ℃ gradually.Add 43 gram furfuryl alcohol resins then, continue down reaction 2 hours, add 95 gram washing oil again at 150 ℃, mix 1 hour after, obtain the black viscous liquid.Recording its viscosity under 75 ℃ is 40 pools.
Embodiment 2:
With 200 gram phenol, 100 milliliters of weight concentrations are that 35% formaldehyde and 0.8 milliliter of weight concentration are that 37% the hydrochloric acid capacity of being added to is in the there-necked flask of 200ml, are heated to backflow, keep this temperature and continue reaction 2 hours.Under normal pressure, distill out the water about 180 milliliters.At the water that steams again under the 0.05MPa vacuum tightness about 20 milliliters.Add 100 gram washing oil, under 0.05MPa vacuum tightness, continue water is steamed, reacting liquid temperature rises to 160 ℃ gradually.Add 200 gram furfuryl alcohol resins then,, add 170 gram washing oil again 150 ℃ of down reactions 3 hours, mix 1 hour after, obtain the black viscous liquid.Recording its viscosity under 25 ℃ is 100 pools.
Embodiment 3
With 350 gram phenol, 300 milliliters of weight concentrations are that 35% formaldehyde and the 4 gram oxalic acid capacity of being added to are in the there-necked flask of 1000ml, are heated to backflow, keep this thermotonus after 2 hours, and muddy the appearance arranged.Remove the water in the reaction system under 0.05MP vacuum tightness, making melt temperature is 60-70 ℃ of linear phenolic resins.All resol dissolves with 300 milliliters of Texacar PCs, add 3 gram salt of wormwood again, after reacting 3 hours under 150 ℃, add 520 gram furfuryl alcohol resins, at 150 ℃, reaction is 2 hours under 0.05MPa vacuum tightness, add 100 gram dimethylbenzene at last, mixed 1 hour, and obtained the black viscous liquid, recording its viscosity under 25 ℃ is 75-80 pools.
Embodiment 4
With 250 gram phenol, 160 gram weight concentration are that 35% formaldehyde and the 4 gram oxalic acid capacity of being added to are in the there-necked flask of 2000ml, and reacting by heating liquid is to refluxing, keep this thermotonus 2 hours.Distill under normal pressure and dewater, further remove the water of system again under 0.05MPa vacuum tightness, add 100 gram carbolineums again, in 0.05MP vacuum tightness, 155 ℃ of following reactions of temperature, limits dewater.Under normal pressure, add 150 milliliters of Texacar PCs and 3 gram salt of wormwood, reacted 3 hours down, add 250 gram sugar alcohol resins again at 160 ℃.140 ℃ of temperature, reaction is 1.5 hours under the 0.05MPa vacuum tightness, adds 150 gram ethylene carbonates at last, mixes 1 hour, obtains a black viscous liquid.Under 25 ℃, viscosity is 75-90 pools.
Magnesia-calcium-carbon brick magnesia-calcium-carbon brick magnesia-calcium-carbon brick magnesia-calcium-carbon brick magnesia-calcium brick magnesia-calcium brick is mainly joined MgO 72.93 65.80 71.9 78.1 76.8 72.64 material component C aO 13.58 12.45 9.8 7.5---% by weight C 8.72 18.22 10.5 7.6 15 18.81 be full of cracks without without without without without without apparent porosity (%) 12 11 2.7 3.8 8 1.8 bulk densities (g/cm) 3.01 2.81 3.08 3.14 3.06 3.0 cold crushing strengths (MPa) 42.1 33.6 43.8 51.5 43.6 45.1 strength at normal temperature (MPa) 4.9---12.0-
Claims (2)
1. one kind is used to make the resinoid bond that fire proof material of furnace lining is used, it is characterized in that this wedding agent is that linear phenolic resin and furane resin are mixed by 20-70: 80-30 weight ratio, add the high boiling solvent of 0.5-1.5 times of linear phenolic resin weight and 0.01-1% additive, copolycondensation is 0.5-4 hours under 120-165 ℃ of temperature and 0.03-0.1Mpa vacuum tightness, with thinner viscosity is transferred to the brown or black viscous liquid that 10-200 pools form;
The molecular weight of described linear phenolic resin is 500-1500, and water content is less than 1% weight;
Described furane resin can be furfuryl alcohol resin or furfuryl resin;
Described high boiling solvent can be that washing oil, carbolineum, ethylene carbonate, Texacar PC or phthalic acid ester class are selected from rutgers, diethyl phthalate, phthalic acid dibutyl ester and dioctyl phthalate;
Described additive can be Phenylsulfonic acid, toluene sulfonic acide, methylsulphonic acid, sulfuric acid, phosphoric acid, aluminum chloride or zinc chloride;
Described thinner can be an aromatic solvent, is selected from toluene, dimethylbenzene, trimethylbenzene, washing oil, carbolineum; Or carbonates, be selected from methylcarbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, Texacar PC; Or the aldehyde esters of gallic acid, be selected from ritalin, vinyl acetic monomer, propyl acetate, N-BUTYL ACETATE, amyl acetate-n, capryl acetate, octyl acetate; Or the phthalic acid ester class, be selected from rutgers, diethyl phthalate, phthalic acid dibutyl ester and dioctyl phthalate.
2. as resinoid bond as described in the claim 2, it is characterized in that described linear phenolic resin can adopt following method preparation:
With formaldehyde and phenol with 0.5-1: 1 mixed in molar ratio, the acid that adds phenol weight 0.1-0.8% be as catalyzer, heating reflux reaction 0.5-4 hour, earlier under normal pressure, distill 1-4 hour under 0.01-0.1MPa vacuum tightness the back, with the generation linear phenolic resin and remove water in the system; Add high boiling solvent again, under 0.05-0.1MPa vacuum tightness, heating makes temperature of reaction be elevated to 140-165 ℃ gradually;
Described acid as catalyzer can be hydrochloric acid, sulfuric acid, oxalic acid or phosphoric acid;
Described high boiling solvent can be washing oil, carbolineum, ethylene carbonate, Texacar PC or phthalic acid ester class, is selected from rutgers, diethyl phthalate, phthalic acid dibutyl ester and dioctyl phthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100841 CN1031833C (en) | 1991-02-09 | 1991-02-09 | Resin binder for refractory materials and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100841 CN1031833C (en) | 1991-02-09 | 1991-02-09 | Resin binder for refractory materials and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064094A CN1064094A (en) | 1992-09-02 |
| CN1031833C true CN1031833C (en) | 1996-05-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100841 Expired - Fee Related CN1031833C (en) | 1991-02-09 | 1991-02-09 | Resin binder for refractory materials and preparing process thereof |
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| CN (1) | CN1031833C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538451B (en) * | 2009-04-29 | 2012-07-25 | 山东莱芜润达化工有限公司 | Anhydrous resin bonding agent for fireproof material and preparation method thereof |
| CN103044046A (en) * | 2013-01-18 | 2013-04-17 | 武汉科技大学 | Curing method for carbon-containing refractory material combined with thermoplastic phenolic resin |
| CN103289618B (en) * | 2013-06-06 | 2015-04-08 | 江苏苏嘉集团新材料有限公司 | Compound modified oxidation-resisting phenolic resin binder and preparation method thereof |
| CN103755360B (en) * | 2013-12-16 | 2015-03-25 | 芜湖市天雄新材料科技有限公司 | Guide rod pouring material of slag blocking plug used for converter tapping slag blocking |
| CN103755356B (en) * | 2013-12-16 | 2015-02-18 | 芜湖市天雄新材料科技有限公司 | Preparation method of guide rod flame-retardant coating high-performance binder |
| CN103755357B (en) * | 2013-12-16 | 2015-03-25 | 芜湖市天雄新材料科技有限公司 | High-performance binder of guide rod flame-retardant coating |
| CN107999737B (en) * | 2017-03-24 | 2020-05-05 | 王世泰 | Preparation process of continuous casting refractory part |
| CN109280519A (en) * | 2018-09-17 | 2019-01-29 | 安徽博耐克摩擦材料有限公司 | The glue and preparation method thereof being bonded for brake block steel back and friction block |
| CN113912801B (en) * | 2021-11-25 | 2023-08-22 | 浙江自立高分子化工材料有限公司 | Anhydrous phenolic resin binder for magnesia-calcium bricks and preparation method thereof |
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1991
- 1991-02-09 CN CN 91100841 patent/CN1031833C/en not_active Expired - Fee Related
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| CN1064094A (en) | 1992-09-02 |
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