CN1205735A - Granular suds suppressing component - Google Patents
Granular suds suppressing component Download PDFInfo
- Publication number
- CN1205735A CN1205735A CN 96199219 CN96199219A CN1205735A CN 1205735 A CN1205735 A CN 1205735A CN 96199219 CN96199219 CN 96199219 CN 96199219 A CN96199219 A CN 96199219A CN 1205735 A CN1205735 A CN 1205735A
- Authority
- CN
- China
- Prior art keywords
- acid
- suds suppressing
- suppressing component
- salt
- anion surfactant
- 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
Landscapes
- Detergent Compositions (AREA)
Abstract
The present invention provides a process for making a highly effective granular suds suppressing component comprising the steps of: (a) intimately mixing a liquid or molten suds suppressing component with an emulsifier to form a premix, and (b) granulating the premix with a powder wherein an anionic surfactant is used as the emulsifier. Furthermore, it is preferred that the granulating powder comprises aluminosilicate.
Description
The present invention relates to preparation method and some granular suds suppressing component of granular suds suppressing component.
Granular suds suppressing component is used for many application, comprises detergent for washing clothes, and wherein it needs control usually or is reduced in the foamy amount that produces in the automatic washing machine.In automatic washing machine, should avoid forming a large amount of foams usually, because this has reduced the efficient of washing process, and, under individual cases, can cause liquid flooding to go out washing machine.
Advised that in the prior art many granular suds suppressing components are with control foam.
On June 13rd, 1979, disclosed GB2009223 disclosed particle polysiloxane/SiO2 froth suppressor, and wherein polysiloxane and nonionogenic tenside (at embodiment 1-3, are TAE25 in 5; Be TAE14 in embodiment 4) pre-mixing, then at carrier substance, for example granulation on phosphoric acid salt, polyphosphate, silicate, silico-aluminate, carbonate, vitriol, multi-carboxylate or the phosphonate.
February 1 nineteen ninety-five, disclosed EP636684 disclosed a kind of Foam Control, and it contains the 1-30% polysiloxane defoamers; The 70-99% zeolite; Polysiloxane copolymer and 1-40% multi-carboxy acid salt washing agent.
Present detergent for washing clothes, especially when using high-load lathering surfactant with the performance that obtains and detersive efficiency, what become more and more important provides more effective suds suppressing component.
The purpose of this invention is to provide the method for preparing the high-efficient granule suds suppressing component, it comprises step:
(a) liquid or fusion suds suppressing component and emulsifying agent are closely mixed with form premixture and
(b) with this premixture of powder granulation.
Summary of the invention
Purpose of the present invention reaches as emulsifying agent by using anion surfactant.In addition, prilling powder preferably contains silico-aluminate.
In a preferred embodiment of the invention, method also comprises the adding structural agent, and it is selected from phosphonic acids and di 2 ethylhexyl phosphonic acid, carboxylic acid and poly carboxylic acid, succsinic acid and disuccinic acid and their salt and their mixture.Hydroxy ethylene diphosphonic acid and poly carboxylic acid or their salt are most preferred structural agents.
In another aspect of this invention, it provides the granular suds suppressing agent, and it contains silicone oil suds suppressing component and anion surfactant.Preferred granular suds suppressing agent contains:
(a) 1% to 40% silicone oil by weight;
(b) 1% to 40% anion surfactant by weight;
(c) 1% to 40% structural agent by weight, it is selected from phosphonic acids and di 2 ethylhexyl phosphonic acid, carboxylic acid and poly carboxylic acid, succsinic acid and disuccinic acid and their salt and their mixture; With
(d) 40% to 97% sodium silicoaluminate by weight.
The most preferred ratio of silicone oil and anion surfactant is 1: 1 to 2: 1.
The detailed description suds suppressor of invention
Various materials can be used as froth suppressor, for example soluble salt, the high-molecular-weight hydrocarbons of mono carboxylic lipid acid and they, for example fatty acid ester of paraffinic hydrocarbon, fatty acid ester, monovalent alcohol, aliphatic C1-C40 ketone, N-alkoxylate aminotriazine, propylene oxide and single stearyl phosphoric acid salt and phosphoric acid ester.Another kind of preferred suds suppressor comprises the polysiloxane inhibitor.Such material comprises use organopolysiloxane oil, the for example dispersion agent of polydimethylsiloxane, polydimethyl siloxane oil or resin or emulsifying agent, with the combination of organopolysiloxane and silica dioxide granule, organopolysiloxane chemisorption or be melted on the silicon-dioxide wherein.Preferred polydimethylsiloxane contains the trimethylsilyl end groups closed cell, has 5 * 10 at 25 ℃
-5m
2/ s-0.1m
2The viscosity of/s is corresponding to the polymerization degree of about 40-1500.Solid silica can be pyrogenic silica, precipitated silica or by the silicon-dioxide of gel formation technology preparation.Silica dioxide granule has 0.1 to 50 micron, preferred 1 to 20 micron average particle size particle size and 50m at least
2The surface-area of/g.These silica dioxide granules can become hydrophobic by being connected to handle on the silicon-dioxide with dialkyl group silyl and/or trialkylsilkl or directly or by polyorganosiloxane resin.The preferred silicon-dioxide that uses its particle to become hydrophobic with dimethyl and/or trimethyl silyl.The polysiloxane defoamers of using in Foam Control of the present invention has the silicon-dioxide of the gross weight 1-30% (more preferably 2-15%) by polysiloxane defoamers suitably, causes polysiloxane defoamers to have 2 * 10
-4m
2/ s-1m
2The average viscosity of/s.Preferred polysiloxane defoamers can have 5 * 10
-3m
2/ s-0.1m
2The viscosity of/s.Even more preferably have 2 * 10
-2m
2/ s-4.5 * 10
-2m
2The polysiloxane defoamers of the viscosity of/s.
Polysiloxane defoamers is known in the prior art, and is for example, open in the US-A 4265779 of promulgation on May 5th, 1981.Other polysiloxane suds suppressor is open in US-A3455839 and German patent application DE-A 2124526.Anion surfactant
Useful anion surfactant also is included in to have in its molecular structure and contains about 10 water-soluble salts to the organosulfur acid-respons product of the alkyl of about 20 carbon atoms and sulfonic acid or sulfate group, preferred as alkali, ammonium and alkanol ammonium salt.(moieties that in term " alkyl ", comprises acyl group).This example that is combined into tensio-active agent is sodium alkyl sulfate and potassium, especially by higher alcohols (C
8-C
18Individual carbon atom) product that sulfation obtains, described the alcohol for example reduction of the glyceryl ester by Tallow, beef or Oleum Cocois obtain; With sodium alkyl benzene sulfonate and potassium, wherein alkyl contains and has an appointment 9 to about 15 carbon atoms, is the straight or branched configuration, for example the product of the type of describing in US2220099 and 2477383.Especially valuable is the linear straight chain alkylbenzene sulfonate, and wherein the average carbon atom number of alkyl is about 11-13, is abbreviated as C
11-C
13LAS.
Other useful anion surfactant is included in to contain in the fatty acid group and has an appointment 6-20 carbon atom and contain the water-soluble salt of ester of the α-alpha-sulfonated fatty acid of 1 to 10 carbon atom of having an appointment in ester group; In acyl group, contain and have an appointment 2-9 carbon atom and in paraffin section, contain the water-soluble salt of 9 the 2-acyloxy-alkane-1-sulfonic acid of having an appointment to about 23 carbon atoms; The sulfated alkyl ether that in alkyl, contains have an appointment 10-20 carbon atom and about 1-30 moles of ethylene oxide; The water-soluble salt that contains the alkene sulfonic acid of 12-24 the carbon atom of having an appointment; Have an appointment 1-3 carbon atom and contain 8 the β-alkoxy alkane sulfonate of having an appointment with in alkyl, containing to about 20 carbon atoms at paraffin section.
Sarcosinate, for example the oil base sarcosinate can be used among the present invention.
What also can be used as the anion surfactant use in the present invention is hydrotropic agent, for example arylsulphonate.The preferably sodium or the sylvite of benzene,toluene,xylene or cumene sulfonic acid.Powder
Many powder are applicable to granulation step of the present invention.The preferred powder that is used for method and composition of the present invention is the mixture of compatible detergent builders or washing assistant or powder.
Detergent composition of the present invention can contain the crystal aluminosilicate ion-exchange material of following formula:
Na
Z{ (AlO
2)
Z(SiO
2)
y] xH
2O wherein z and y is at least about 6, and the mol ratio of z and y is about 1.0 to about 0.4, and x is about 10 to about 264.Be used for amorphous hydrated silico-aluminate material of the present invention and have following empirical formula:
M
z(zAlO
2YSiO
2) wherein M be the ammonium of sodium, potassium, ammonium or replacement, z is about 0.5 to about 2, y is 1, described material has the magnesium ion exchange capacity at least about 50 milligramequivalent calcium carbonate hardness/anhydrous silico-aluminate of every gram.Grain sizes is about 1 to 10 micron hydration natrolite A.
Silico-aluminate ion-exchange builder material of the present invention is a hydrated form, if crystallization contains about by weight 10 to about 28% water, if unbodied, contains the more water of volume potentially.Highly preferred crystal aluminosilicate ion exchange material contains 18% to about 22% the water of having an appointment in its crystalline matrix.The crystal aluminosilicate ion exchange material is further characterized in that its particle size diameter is about 0.1 micron to about 10 microns.Amorphous substance is normally less, for example less than about 0.01 micron.Preferred ion exchange material have about 0.2 micron to about 4 microns particle size diameter.Term of the present invention " particle size diameter " expression is by the average particle size particle size diameter of the weight of certain ion exchange material, and it for example uses the measurement microscope method of scanning electronic microscope by the routine analysis technology.Another of common crystal aluminosilicate ion exchange material of the present invention is characterised in that their calcium ion exchange capacity, based on anhydrous benchmark, it is at least about 200mg equivalent calcium carbonate water hardness per gram silico-aluminate, and it is generally about 300mgeq/g to about 352mgeq/g.The calcium ion exchange rate that is further characterized in that them of silico-aluminate ion exchange material of the present invention is at least about 2 grain Ca
++/ gallon per minute/gram/gallon (anhydrous benchmark) based on hardness ions hardness, is generally about 2 grain Ca
++/ gallon per minute/gram/gallon is to about 6 grain Ca
++/ gallon per minute/gram/gallon.Be used as the calcium ion exchange rate of the best silico-aluminate demonstration of washing assistant purposes at least about 4 grains/gallon per minute/gram/gallon.
The amorphous aluminosilicate ion exchange material has the (12mgMg at least about 50mgeq. lime carbonate/g usually
++/ g) Mg
++Exchange and at least about the Mg of 1 grain/gallon per minute/gram/gallon
++Rate of exchange.When checking amorphous substance, do not show observable diffraction pattern with copper radiation (1.54 atomic meter).
It is commercial available being used for silico-aluminate ion exchange material of the present invention.Being used for silico-aluminate of the present invention structurally can be crystalline or unbodied, can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing the silico-aluminate ion exchange material is described in the US3985669 of the Krummel of promulgation on October 12nd, 1976 etc., and this patent is classified this paper reference as.Preferred synthetic crystallization silico-aluminate ion exchange material useful among the present invention can obtain with title zeolite A, zeolite B, zeolite P, zeolite MAP and X zeolite.In especially preferred embodiment, the crystal aluminosilicate ion exchange material has following formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein x is about 20 to about 30, and is preferred about 27, has usually to be lower than about 5 microns particle size.
Granulated detergent of the present invention can contain neutrality or basic salt, and it can have 7 or bigger pH in solution, can be inorganic or organic in nature.Builder salt helps to provide required density and tap density to detergent particles of the present invention.Although some salt is inert, their many detergent builder compounds that in washing soln, also play a part.
The example of neutral water-soluble salt comprises muriate, fluorochemical and the vitriol of the ammonium of basic metal, ammonium or replacement.Above-mentioned an alkali metal salt, especially sodium salt are preferred.
Other useful water-soluble salt comprises known compound as the detergent builder material usually.Washing assistant is selected from the ammonium salt of various water-soluble alkalis, ammonium or the replacement of phosphoric acid, Tripyrophosphoric acid, carbonic acid, boric acid, silicic acid and poly-hydroxy sulfonic acid usually.Preferred above-mentioned an alkali metal salt, especially sodium salt.
The specific examples of inorganic phosphate builders is that tripolyphosphate, tetra-sodium, the polymerization degree are about 6 to 21 poly-metaphosphoric acid and ortho-phosphoric sodium and sylvite.
The example of non-phosphorus inorganic builders is the sodium and the sylvite of carbonate, supercarbonate, sesquicarbonate, tetraborate decahydrate.Structural agent
Being used for structural agent of the present invention is phosphonic acids and di 2 ethylhexyl phosphonic acid, carboxylic acid and poly carboxylic acid, succsinic acid and disuccinic acid and their salt and their mixture.
The preferred construction agent is a phosphonate, for example sodium of ethylidene diphosphonic acid and sylvite, ethane 1-hydroxyl-1, the sodium of 1-diphosphonate and sylvite and ethane-1,1, the sodium of 2-tri methylene phosphonic acid and sylvite.Especially preferred is hydroxy ethylene diphosphonic acid and diethylenetriamine five (methylene phosphonic acid).
Another kind of or other preferred construction agent is a carboxylic acid, for example the homopolymer of aliphatic carboxylic acid such as vinylformic acid, toxilic acid, hexenoic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.The multipolymer of acid form or neutral vinylformic acid and toxilic acid most preferably.Other multi-carboxylate illustrates in the US3308067 of the Diehl of promulgation on March 7th, 1967.
Another kind of or other preferred construction agent is a succsinic acid, quadrol-N for example, the ammonium salt of N '-disuccinic acid (EDDS) or their basic metal, alkaline-earth metal, ammonium or replacement or their mixture.Preferred EDDS compound is free acid form and their sodium or magnesium salts.The example of this preferred EDDS sodium salt comprises NaEDDS, Na
2EDDS and Na
4EDDS.The example of this preferred EDDS magnesium salts comprises MgEDDS and Mg
2EDDS.
More detailed description by the method for the synthetic EDDS of industrial obtainable starting material is seen the Kezerian of promulgation on November 24th, 1964 and the US3158635 of Ramsay.
Synthesize EDDS owing to two unsymmetrical carbons by maleic anhydride and quadrol, generate the mixture of three optically active isomers [R, R], [S, S] and [S, R].The biological degradation of EDDS is that optically active isomer is selected, and [S, S] isomer degraded is the fastest and the most completely, and for this reason, [S, S] isomer is most preferred in composition of the present invention.
[S, S] isomer of EDDS can be synthetic, as follows by L-aspartic acid and glycol dibromide:
2CH
2--CH--NH
2+Br-CH
2-CH
2-BR?NaOH?[s，s]EDDS
COOH?COOH
The reaction of L-aspartic acid and glycol dibromide is seen Neal and Rose " the Stereoselective ligand of ethylenediamine disuccinic acid and their title complex " with the more complete description of [S, S] isomer of forming EDDS,
Inorganic chemistry, the 7th volume (1968), 2405-2412 page or leaf.
Another kind or other preferred structure agent are Citrate trianion and silicate, and the mol ratio of its silicon-dioxide and alkalimetal oxide is about 0.5 to about 4.0, preferred about 1.0 to about 2.4.Particle size
The average particle size particle size of granular suds suppressing component is 400-800, preferred 450-650 micron.Especially when using the paradigmatic structure agent, for example during vinylformic acid-maleic acid, avoid little particle (less than 400 microns).In this case, little particle causes gelationization when contacting with water, and it has disadvantageous effect to foam control.This can or not exist under the anion surfactant emulsifying agent in existence and occurs.Big particle can cause separating, thereby preferably avoids.The method for preparing foam inhibition component
Many prilling process can use to prepare granular suds suppressing component of the present invention.The selection of prilling process is mainly by the definite character decision of the component of granulation.
In a preferred embodiment of the invention, can be based on the foam inhibition component of silicone oil easily by following method granulation.The polysiloxane suds suppressor at first with anion surfactant pre-mixing under 50-80 ℃ temperature.Anion surfactant can be used as the aqueous solution or thickness soup compound or uses as powder.Premixture mixes with the structural agent of the aqueous solution preferably subsequently.The mixture that generates last with cause forming the particulate powder mixes.High-shear mixer is particularly suitable for this granulation step, for example laboratory scale food-processor or pilot plant or plant-scale Schugi or Loedige mixing tank.Particle is used dry air drying subsequently under 25 ℃ of temperature in fluidized bed dryer.
In another embodiment, the aqueous solution pre-mixing of foam inhibition component of polysiloxane and structural agent.The anion surfactant of powder type and detergent powder (crystal aluminosilicate) pre-mixing, structurized subsequently moisture polysiloxane premixture and the granulation in aforesaid high-shear mixer of powder premixture.
The particle that obtains is crisp and free-pouring.Embodiment
Particle froth suppressor with composition of following embodiment 1-10 prepares by the following method.Little laboratory scale food mixer is used to be mixed and heated to polysiloxane/silicon-dioxide defoaming compounds and tensio-active agent of 60 ℃.Add structural agent then, liquid mixture closely mixed 2-3 minute with zeolite in the full speed food mixer subsequently.Add additional water individually and form to finish particle, then particle in fluidized-bed with the pressurization dry air drying of 4bar and 25 ℃ 20-30 minute to form final free flowing granule.
The water 11.7 5.9 3.1 5.8 16.2 that embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 silicone oil/silica 9.9 10.4 8.6 10.2 9.4 anion surfactant 13.2 15.5 32 16.9 12.5 Wessalith CSs, 59.3 62 51.2 61 56.3 hydroxy ethylene diphosphonic acids 5.9 6.2 5.1 6.1 5.6 (28% living solution) add
The anion surfactant that uses in embodiment 1 to 5 is:
It in embodiment 1 90% reactive powder of alkyl-sulphate;
It in embodiment 2 78% active alkyl-sulphate/alkyl ethoxylated sulfate soup compound;
It in embodiment 3 32% active aqueous slurry of Tallow, beef alkyl-sulphate;
It in embodiment 4 72% active aqueous slurry of alkyl-sulphate;
It in embodiment 5 90% reactive powder of secondary alkyl sulfate.
The water 3.7 3.7 3.4 2.4 3.4 that embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 silicone oil/silica 1 0.3 10.9 11 10.6 11 linear alkylbenzene sulfonate (LAS) 15.9 16.8 17 16.6 17 (78% slurry) Wessalith CSs 63.5 62 62.1 62.8 62.1 structural agents 6.3 6.6 6.5 7.6 6.5 add
The structural agent that uses in embodiment 6-10 is:
It in embodiment 6 28% living solution of hydroxy ethylene diphosphonic acid;
In embodiment 7 water of 28% diethylenetriamine five (methylene phosphonic acid) sodium salt, 6% vinylformic acid-maleic acid, 6% sal epsom and 60%;
It in embodiment 8 40% living solution of Trisodium Citrate;
In embodiment 9 S, S quadrol N, 15% sodium salt of N disuccinic acid, 15% sal epsom and 60% water;
In embodiment 10 S, S quadrol N, 30% living solution of N disuccinic acid sodium salt.
Claims (10)
1. method for preparing granular suds suppressing component, it comprises step:
(a) liquid or fusion suds suppressing component and emulsifying agent are closely mixed with form premixture and
(b) with this premixture of powder granulation,
It is characterized in that emulsifying agent is an anion surfactant.
2. according to the process of claim 1 wherein that powder contains silico-aluminate.
3. according to the method for claim 1 or 2, wherein premixture also contains structural agent, and it is selected from phosphonic acids and di 2 ethylhexyl phosphonic acid, carboxylic acid and poly carboxylic acid, succsinic acid and disuccinic acid and their salt and their mixture.
4. according to the method for claim 3, wherein structural agent is hydroxy ethylene diphosphonic acid or its salt.
5. according to the method for claim 3, wherein structural agent is poly carboxylic acid or its salt.
6. according to the method for claim 5, wherein the average particle size particle size of granular suds suppressing component is at least 450 microns.
7. according to the process of claim 1 wherein that suds suppressing component contains silicone oil.
8. granular suds suppressing component, it contains:
(a) silicone oil is characterized in that component also contains
(b) anion surfactant.
9. granular suds suppressing component according to Claim 8, it contains:
(a) 1% to 40% silicone oil by weight;
(b) 1% to 40% anion surfactant by weight;
(c) 1% to 40% structural agent by weight, it is selected from phosphonic acids and di 2 ethylhexyl phosphonic acid, carboxylic acid and poly carboxylic acid, succsinic acid and disuccinic acid and their salt and their mixture; With
(d) 40% to 97% sodium silicoaluminate by weight.
10. according to Claim 8 or 9 granular suds suppressing component, wherein the ratio of silicone oil and anion surfactant is 1: 1 to 2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96199219 CN1205735A (en) | 1995-11-03 | 1996-10-25 | Granular suds suppressing component |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95202988.2 | 1995-11-03 | ||
| CN 96199219 CN1205735A (en) | 1995-11-03 | 1996-10-25 | Granular suds suppressing component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1205735A true CN1205735A (en) | 1999-01-20 |
Family
ID=5129374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96199219 Pending CN1205735A (en) | 1995-11-03 | 1996-10-25 | Granular suds suppressing component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1205735A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104703666A (en) * | 2012-10-11 | 2015-06-10 | 道康宁公司 | Anti-foaming agent and pulp preparation method |
-
1996
- 1996-10-25 CN CN 96199219 patent/CN1205735A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104703666A (en) * | 2012-10-11 | 2015-06-10 | 道康宁公司 | Anti-foaming agent and pulp preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6052192B2 (en) | detergent composition | |
| CN1132526A (en) | Process for making high density detergent agglomerates | |
| CN1042744C (en) | Foam Control agent in granular form | |
| EP0970017B1 (en) | Novel hybrid zeolite-silica compositions | |
| WO1998015610A1 (en) | Detergent composition | |
| CN1075162A (en) | Has the deliquescent granular laundry compositions of enhancing | |
| CN1047792C (en) | A granular detergent component and a granular detergent composition containing the same | |
| CN1101463C (en) | Process for preparing granular detergent components or compositions | |
| WO1997016519A1 (en) | Granular suds suppressing component | |
| CN1117849C (en) | Process for preparing granular detergent components | |
| CN1205735A (en) | Granular suds suppressing component | |
| CN1174566A (en) | Detergent composition containing cationic surfactant and its preparation method | |
| EP0050897B1 (en) | Aluminosilicate-agglomerates and detergent compositions containing them | |
| EP0266931A1 (en) | Granular detergents which contain high levels of anionic surfactant | |
| CN1202195A (en) | Process for making granular detergents | |
| US6004921A (en) | Process for making granular suds suppressing component | |
| CN1150449A (en) | Process for manufacture of free-flowing detergent granules | |
| CN1160600A (en) | Process of producing fine-grain Model. A zeolite | |
| CN1168690A (en) | Detergent composition containing zeolite MAP builder | |
| CN1230981A (en) | Preparation of low density detergent agglomerates containing silica | |
| CN1269823A (en) | Process for making high-activity detergent agglomerates by multi-stage surfactant paste injection | |
| WO2001070630A2 (en) | A method of forming high aluminum aluminosilicate zeolites, microcrystalline zeolites and macroscopic aggregates thereof | |
| US5925614A (en) | Process for producing granular detergent components or compositions | |
| US6140301A (en) | Process for producing granular detergent components or compositions | |
| Christophliemk et al. | Zeolites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |