CN1432279A - Delayed release biocide - Google Patents
Delayed release biocide Download PDFInfo
- Publication number
- CN1432279A CN1432279A CN 02100331 CN02100331A CN1432279A CN 1432279 A CN1432279 A CN 1432279A CN 02100331 CN02100331 CN 02100331 CN 02100331 A CN02100331 A CN 02100331A CN 1432279 A CN1432279 A CN 1432279A
- Authority
- CN
- China
- Prior art keywords
- glycolylurea
- delayed release
- biocide
- bromine
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 19
- 239000003139 biocide Substances 0.000 title claims abstract description 18
- 230000003111 delayed effect Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims description 12
- MBLGNFCFUOLRJX-UHFFFAOYSA-N ClN(C(=O)N(C)C)C(CO)=O.[Br] Chemical compound ClN(C(=O)N(C)C)C(CO)=O.[Br] MBLGNFCFUOLRJX-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000004823 Reactive adhesive Substances 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 7
- -1 hydantoin halides Chemical class 0.000 claims description 7
- 150000001804 chlorine Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229940091173 hydantoin Drugs 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract description 2
- 239000008235 industrial water Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- PQRDTUFVDILINV-UHFFFAOYSA-N bcdmh Chemical compound CC1(C)N(Cl)C(=O)N(Br)C1=O PQRDTUFVDILINV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002070 germicidal effect Effects 0.000 abstract 1
- 150000001469 hydantoins Chemical class 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000001954 sterilising effect Effects 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 235000017168 chlorine Nutrition 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KHILXFJYVGQZFR-UHFFFAOYSA-N ClC(C(=O)NC(=O)N(C)C)(O)Cl Chemical compound ClC(C(=O)NC(=O)N(C)C)(O)Cl KHILXFJYVGQZFR-UHFFFAOYSA-N 0.000 description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 241000295146 Gallionellaceae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical class [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The slow release bromide biocide for disinfection of industrial water and public places consists of bromochloro dimethyl hydantoin as main component 50-80 wt%, other halogenated hydantoin as supplementary material 15-35 wt% and active adhesive 5-15 wt%, and is prepared into tablet or granule with controlled dissolving rate and thus delayed release function. It has the germicidal advantage of bromide biocide maintained and prolonged biocidal effect. Its slow release function is realized through both stepped reaction to release active components slowly and properly selected adhesive to control dissolving rate.
Description
Technical field
The present invention relates to the sterilization processing in industry water field and the sterilization field of public place, (also being suitable for such as swimming pool, toilet, hotel etc.) specifically, is a kind of slowly-releasing bromine class biocide of oxidized form.
Background technology
Based on the biocide of bromine,, adopted by industrial water system gradually because of characteristics such as its consumption are low, effective, environmentally friendly.Early stage, there was the potential safety hazard on using in the product bromine chloride, because then can cause potential safety and harm just in case the leakage of gaseous oxidizer has taken place; There is the bad control of proportioning again in the bromine chloroformate mixture, influence problems such as bactericidal effect, has restricted their development in application.
Summary of the invention
The object of the present invention is to provide:
1 handling safety, convenience, effect stability.The present invention is with the tablet of solid or particle form, impacts or adds continuously, has avoided the destabilizing factor of medicament on safety and effect in the past;
2 reduce the water treatment expense.Slow release effect can give full play of the usefulness of medicament itself, low dosage, and long-acting bactericidal reduces common biocide and adds excessive waste;
A kind of delayed release biocide
The present invention is achieved in that
The present invention is a host with bromine Chlorodimethyl glycolylurea, the hydantoin halides that is equipped with other is done assistant agent, add reactive adhesive again, bromine Chlorodimethyl glycolylurea: assistant agent: reactive adhesive=50～80: 15～35: 5～15 by the control dissolution velocity, makes delayed release biocide with the form of tablet or particle.
Host bromine Chlorodimethyl glycolylurea synthetic is with 5,5-dimethyl hydantion and liquid bromine, liquid chlorine successively alkali lye as disacidify agent effect under, carry out two sections halogenations of N1, N3-and generate through low temperature, reaction equation is as follows:
Assistant agent can be hydantoin halides, chlorine class biocide, i.e. Babysafe, chlorine class glycolylurea.
Reactive adhesive can be the first and second basic glycolylurea classes, simple binder one or more.
Effect of the present invention
1. medicament of the present invention is that the solid form with tablet or particle adds, and no matter is to impact to add or add continuously, and more than bromine chloride or other pressed powder safety, convenience, effect is also stablized in the operation.
Since medicament of the present invention solvability 0.2% in water, but, the good sterilization effect is just arranged at low concentration 5ppm, cooperate suitable doser with tablet form, add better effects if continuously.The static sterilization of laboratory evaluation bactericidal effect 20ppm kept sterilizing rate more than 90% in 72 hours.Bactericidal effect and slow release effect such as table 1, table 2.
The sterilizing rate of table 1 different strain
| Bacterial classification | Sterilizing rate % | Initial bacterium several/ml | |
| Invention medicament 20mg/L | Babysafe 50mg/L | ||
| Heterotroph | ????99.7 | ????99.3 | ????4.6×10 7 |
| Iron bacteria | ????98.9 | ????95.2 | ????5.3×10 5 |
| Sulfate reducing bacteria | ????100 | ????95.1 | ????7.8×10 4 |
Table 2 long-acting bactericidal action time
| The medicament title | 5.4 * 107/ml of the original bacterium of sterilizing rate % |
| ?1h?????4h??????8h??????12h?????24h?????48h????72h | |
| Invention medicament 20mg/L Babysafe 50mg/L | ?99.2???99.2????99.6????98.9????98.6????97.8???92.4 ?99.3???99.6????99.5????96.7????67.5????-??????- |
The present invention, has overcome the shortcoming of product in earlier stage, handling safety, convenience at the advantage while that keeps the bromine bactericide.Particularly increased the function of slowly-releasing, it is low to make sterilization add dose, but the bactericidal action longer duration, can give full play to the sterilizing function of biocide in application process.Principle is the hydrolysis in water of bromine chlorine class glycolylurea, discharges bromine and chlorine with hypobromous acid and hypochlorous form.Discharge the almost very fast generation of reaction of bromine, and the reaction of release chlorine is very slow, the reaction of bromide ion and hypochlorous acid or hypochlorite also takes place generate active very high hypobromous acid in water.Hypobromous acid is the crucial active component of killing microorganisms.Realize that slow-release function one is to utilize its stepwise reaction slowly to discharge active component, the 2nd, select suitable binder, the control dissolution velocity.Concrete enforcement
Bromine Chlorodimethyl glycolylurea: auxiliary material (chlorine class biocide such as Babysafe, chlorine class glycolylurea etc.): reactive adhesive (the first and second basic glycolylurea classes, simple binder one or more etc.)=50～80: 15～35: 5～15.
Host bromine Chlorodimethyl glycolylurea synthetic is with 5,5-dimethyl hydantion and liquid bromine, liquid chlorine successively alkali lye as disacidify agent effect under, carry out two sections halogenations of N1, N3-and generate through low temperature.Because the solvability of target product in water is very little, more complete for what reaction was carried out, select phase transfer catalyst, can improve the yield of product on the one hand, brought convenience also on the other hand the control temperature.
Reaction equation is as follows:
Production process is an intermittent operation, (intermediate products dichloro-dimethyl glycolylurea or dibromo dimethyl hydantoin also can become product separately or as auxiliary material) is with a certain amount of 5,5-dimethyl hydantion, phase transfer catalyst and water add in the synthesis reactor, stir, under nearly freezing point temperature, successively react with simple substance and simple substance chlorine, strict control temperature and charging rate are finished until reaction.Filter then, the washing reaction product, with filter cake fragmentation, the oven dry after the washing, weigh, add some auxiliary materials and reactive adhesive again, or make particle or break into tablet, product.
Seven embodiment
Embodiment one
With bromine Chlorodimethyl glycolylurea: clorox: the proportioning of dichloromethane ethylhydantoin=65: 20: 15, tablet is made in drying, granulation, is applied in the disinfection system before water in the oil refining water field is back to use the cycle water field.The reusing sewage amount 20m of this system
3/ h, heterotroph is 10 before the sterilization
4～10
5Between, seriously exceeded the index 10 of supplementing water
2Individual/ml, dosing takes on-line continuous to add, and the control chlorine residue is at 0.2～0.3mg/L, and the heterotroph index reaches 10
2Individual/below the ml.Satisfied the requirement of circulation.
Embodiment two
With bromine Chlorodimethyl glycolylurea: the dichloro-dimethyl glycolylurea: the proportioning of dichloromethane ethylhydantoin=75: 10: 15 is mixed the back drying-granulating through solid blender, the formation product.The catalysis water field of one oil plant, because system leak is frequent, the water quality vicious circle, once cooperated 1227 alternately to add the control bacterium with Babysafe, liquid chlorine, bacterium index qualification rate only was about 50% in every month, added 2 hours liquid chlorines sometimes, and the cycle water residual chlorine reaction has only 0.1mg/L.After use chlorine dioxide again instead and do oxidative bactericide, effect also loses and is clearly better.Again because system possesses the very big 5000m of the water yield
3, can not do the sterilization of system continually and peel off a large amount of conversion in back water body, made one month experiment of the granule of medicament of the present invention.Add 10ppm later every day with 20ppm impact adding in first day, the heterotroph basic controlling is 10
5In individual/ml, bacterium index qualification rate reaches more than 85%.Embodiment three
With bromine Chlorodimethyl glycolylurea: the dichloro-dimethyl glycolylurea: the proportioning of ethyl cellulose=80: 13: 7 is through the solid blender mixed material, and the drying granulation breaks into tablet again, forms product.
Claims (4)
1. delayed release biocide, it is characterized in that: with bromine Chlorodimethyl glycolylurea is host, the hydantoin halides that is equipped with other is done assistant agent, add reactive adhesive again, bromine Chlorodimethyl glycolylurea: assistant agent: reactive adhesive=50～80: 15～35: 5～15 by the control dissolution velocity, makes delayed release biocide with the form of tablet or particle.
2. a kind of delayed release biocide according to claim 1, it is characterized in that: host bromine Chlorodimethyl glycolylurea synthetic, be with 5,5-dimethyl hydantion and liquid bromine, liquid chlorine successively alkali lye as disacidify agent effect under, carry out two sections halogenations of N1, N3-and generate through low temperature, reaction equation is as follows:
3. a kind of delayed release biocide according to claim 1 is characterized in that: assistant agent can be hydantoin halides, chlorine class biocide, i.e. Babysafe, chlorine class glycolylurea.
4. a kind of delayed release biocide according to claim 1 is characterized in that: reactive adhesive can be the first and second basic glycolylurea classes, simple binder one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100331 CN1432279A (en) | 2002-01-11 | 2002-01-11 | Delayed release biocide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100331 CN1432279A (en) | 2002-01-11 | 2002-01-11 | Delayed release biocide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1432279A true CN1432279A (en) | 2003-07-30 |
Family
ID=27627051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02100331 Pending CN1432279A (en) | 2002-01-11 | 2002-01-11 | Delayed release biocide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1432279A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7172782B2 (en) | 2001-06-28 | 2007-02-06 | Albemarle Corporation | Microbiological control in poultry processing |
| US7182966B2 (en) | 2001-06-28 | 2007-02-27 | Albemarle Corporation | Microbiological control in poultry processing |
| US7901276B2 (en) | 2003-06-24 | 2011-03-08 | Albemarle Corporation | Microbiocidal control in the processing of meat-producing four-legged animals |
| US7914365B2 (en) | 2005-12-01 | 2011-03-29 | Albemarle Corporation | Microbiocidal control in the processing of meat-producing four-legged animals |
| US7999118B2 (en) | 2000-01-18 | 2011-08-16 | Albemarle Corporation | Process for producing N-halogenated hydantoins |
| CN102246751A (en) * | 2011-05-18 | 2011-11-23 | 上海未来企业有限公司 | Sterilizing synergistic agent for oxidizing biocide |
-
2002
- 2002-01-11 CN CN 02100331 patent/CN1432279A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7999118B2 (en) | 2000-01-18 | 2011-08-16 | Albemarle Corporation | Process for producing N-halogenated hydantoins |
| US8586763B2 (en) | 2000-01-18 | 2013-11-19 | Albemarle Corporation | Process for producing N-halogenated hydantoins |
| US9029562B2 (en) | 2000-01-18 | 2015-05-12 | Albemarle Corporation | Process for producing N-halogenated hydantoins |
| US7172782B2 (en) | 2001-06-28 | 2007-02-06 | Albemarle Corporation | Microbiological control in poultry processing |
| US7182966B2 (en) | 2001-06-28 | 2007-02-27 | Albemarle Corporation | Microbiological control in poultry processing |
| US7767240B2 (en) | 2001-06-28 | 2010-08-03 | Albemarle Corporation | Microbiological control in poultry processing |
| US7901276B2 (en) | 2003-06-24 | 2011-03-08 | Albemarle Corporation | Microbiocidal control in the processing of meat-producing four-legged animals |
| US7914365B2 (en) | 2005-12-01 | 2011-03-29 | Albemarle Corporation | Microbiocidal control in the processing of meat-producing four-legged animals |
| CN102246751A (en) * | 2011-05-18 | 2011-11-23 | 上海未来企业有限公司 | Sterilizing synergistic agent for oxidizing biocide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH05500771A (en) | Calcium hypochlorite composition for preventing scale formation and method of using the same | |
| US6641828B1 (en) | Methods for microbiological control in aqueous systems | |
| US11019823B2 (en) | Method of controlling water surface inhabiting pests | |
| CN101293689B (en) | Water treatment medicament | |
| CN102422841A (en) | Reactive chlorine dioxide powder and preparation method thereof | |
| CN101585576A (en) | Water environment improver for aquiculture | |
| CN1432279A (en) | Delayed release biocide | |
| CN102197830B (en) | Composite sanitizer tablet containing trichloroiminocyanuric acid (TCCA) and preparation method thereof | |
| CN100562517C (en) | Process for the industrial production of powder, granule and flake BCH disinfectants | |
| CN102234598A (en) | Common jasminorange leaf and twig flower-jasmine flower phosphorous-free perfumed washing powder | |
| CN1161140A (en) | Self-removed, quick dissolved, quick effect double layer disinfecting tablet and process for producing same | |
| CN1907872A (en) | Water quality modifying agent | |
| CN101785478B (en) | Preparation method of zeolite-loaded potassium permanganate algicide and method for controlling and removing algae | |
| US20040082632A1 (en) | Methods for microbiological control in aqueous systems | |
| US5330676A (en) | Chloroisocyanurate compositions which rapidly disintegrate | |
| CN108094420A (en) | The preparation method of modified konjac glucomannan supported copper sustained release agent and the application in wawter bloom control | |
| CN106620795A (en) | Nanoscale air purifying agent and preparation method thereof | |
| CN1051750C (en) | Application and its using method of biological decontaminant in circulation water system | |
| CN1208760A (en) | No environmental pollution synthetic detergent | |
| CN102657173A (en) | 1-bromo-3-chloro-5, 5-dimethyl hydantoin and 1, 3-dichloro-5, 5-dimethyl hydantoin compound disinfection tablet and method for preparing same | |
| KR0178333B1 (en) | Bacillus bacterium and bactericide and preparation method thereof | |
| CN1043295C (en) | Prescription for plant drop disease with special effectiveness | |
| CN109321384A (en) | detergent composition | |
| CN114180667A (en) | Preparation method of efficient phosphorus removal agent | |
| CN102234591A (en) | Phosphorus-free fragrant washing powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |