CN1258586C - Detergent bar composition and process for its manufacture - Google Patents
Detergent bar composition and process for its manufacture Download PDFInfo
- Publication number
- CN1258586C CN1258586C CNB028220234A CN02822023A CN1258586C CN 1258586 C CN1258586 C CN 1258586C CN B028220234 A CNB028220234 A CN B028220234A CN 02822023 A CN02822023 A CN 02822023A CN 1258586 C CN1258586 C CN 1258586C
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- China
- Prior art keywords
- detergent
- detergent bar
- bar
- composition
- active material
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0069—Laundry bars
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
A detergent bar comprising: (i) from 5% to 60%, preferably from 10% to 50% by weight of detergent active; and(ii) from 2% to 20%, preferably from 5% to 15% by weight of a structuring system being the reaction product of at least two different polyvalent metal ions with sodium silicate, wherein one of the metal ions is calcium or magnesium and the other being selected from boron, aluminium, zinc, calcium and magnesium.
Description
Invention field
The detergent bar composition and the manufacturing thereof that the present invention relates to the washing of confession fabric and use for surface cleaning.The invention particularly relates to and allow higher water of constitution content but have gratifying processing characteristics and the detergent bar of necessary machinery of terminal user's characteristic and constitutional features.
Background of invention
Detergent bar will have acceptable physical strength, so that they keep the complete of its structure in processing, transportation and use.It after the hardness of this stripe shape agent reaches during fabrication the parameter of a particularly important.The stripe shape agent is harder to include the stripe shape agent that some composition produces higher density usually in order to make, and makes that this stripe shape agent is littler significantly and therefore the human consumer is lacked magnetism, and more difficult and often contain the sensation of sand in addition in the fabric washing.Commercially available detergent bar contains washing composition activeconstituents and detergent component, together with containing conventional composition, for example abrasive material, filler, spices, basic salt and SYNTHETIC OPTICAL WHITNER.
In various product forms such as preparation clean synthetics such as liquid, powder, gel, bar, sheet, cake, simple type, stripe shape, sheet type or simple type are better than other type economically.Compare to other pattern, for example paste, gel or powder, the batching of stripe shape product is subjected to strict control.The stripe shape product also is difficult for drenched and the composition that loses activity in the presence of water.But, for the product of making solid form will need to prepare specific composition and control processing.
GB-A-209 013 discloses detergent bar composition, produces with this stripe shape agent composition by mix the silico-aluminate parent under alkaline condition, and silico-aluminate just forms on the spot like this.
IN-A-171 326 discloses a kind of two component stiffening systems, comprises polyvalent metal compounds and material, and here, one of these compositions are essential at least before the active substance neutralization exists.The polyvalent metal compounds that this patent relates to is the salt of aluminium, magnesium, boron and the salt of IIa and IIb family.These stripe shape agent have improved hardness, serviceability ratio and mashed prod characteristic.
GB-A-256 647 discloses the method that forms the agent of low density stripe shape, in the silicate part with before the active substance starch is pre-mixed with the detergent active material of acid form at least here.If the starch of near small part adds before neutralization, just this prescription produces the stripe shape agent that does not contain sand so.Used starch is native starch in this patent.This starch just forms the low density stripe shape agent with excellent processing characteristics in conjunction with the silica that produces on the spot.
We have found a kind of new method to produce the detergent bar of advantageous characteristic, for example good processing characteristics, service performance and improved hydropexis capacity.This realizes that with the structural system that forms on the spot that the water glass reaction obtains wherein a metal ion is calcium or magnesium by making at least two kinds of different polyvalent metal ions, and another can be arbitrary boron, aluminium, diction, calcium or magnesium.
China clay (hydrated aluminium silicate) is the filler of using always and can be attached in the stripe shape agent so that hardness to be provided.Therefore removing china clay in prescription just makes this stripe shape agent softer.But it is desirable removing china clay for the event of environmental protection, because china clay contains trace heavy metals.From the viewpoint of aesthetics, remove china clay and make more optics of this stripe shape agent again.Another object of the present invention is the stripe shape agent of the no any china clay of preparation, and the brightness that still keeps the hardness of this stripe shape agent and improve this stripe shape agent.
A kind of detergent bar composition is provided according to an aspect of the present invention, comprises:
(i) be 5% to 60% by weight, be preferably 10% to 50% detergent active material;
Be 2% to 20% by weight (ii), be preferably at least two kinds of different polyvalent metal ions of 5% to 15% structural system with the reaction product of water glass, wherein a metal ion is calcium or magnesium, and another then is selected from boron, aluminium, zinc, calcium and magnesium.
According to a second aspect of the invention, provide a kind of method of making the detergent bar composition of first aspect present invention, the step that this method comprises is:
(i) in the composition that comprises some this detergent active material at least or its acid parent, make at least two kinds of different polyvalent metal ions, at acid parent fraction or before all neutralizing, in the N-process and/or after the neutralization, generating structure system with water glass reaction and on the spot, one of metal ion is calcium or magnesium, and another then is selected from boron, aluminium, zinc, calcium and magnesium;
(ii) randomly step (i) before, in the process and/or add other composition afterwards, for example other detergent active material, component, filler, and other conventional ingredient;
(iii) resulting block is converted to the product form of hope.
The weight percent of structural system in this synthetics is 2% to 20%.This structural system is preferably in the acid parent of detergent active material and the back forms.
By the method for any routine, for example mold pressing and punching press can convert resulting block to the product form of hope easily.
Detailed Description Of The Invention
Detergent active material
Detergent active material is selected from soap or non-soap active substance, and preferably negatively charged ion that is used for detergent bar technology described in the document and specific detergent active material, for example tensio-active agent that Schwartz, Perry and Berch showed and washing composition, volume II (intermediate science press, New York, 1958).
The specific examples that can be used for suitable anion active substance of the present invention is soap or non-soap, is selected from straight chain and branch-alkylbenzene sulfonate, sulfonated alkane, secondary alcohol sulfate, primary alcohol sulfate,, sulfonated, sulfated alkyl ether, fatty acyl group sulfonated ester, alkyl carboxylate and these mixture.
When detergent active material is soap, uses usually the term total fatty material of TFM slightly to represent the lipid acid that exists in the soap and the weight percent of triglyceride level nubbin, and do not consider the positively charged ion followed.
For the soap that contains 18 carbon atoms, the sodium cation weight of following generally will be equivalent to about 8%.Other positively charged ion can arbitrarily be applied, for example zinc, potassium, magnesium, alkylammonium and aluminium.
The term soap is represented the salt of carboxylic fatty acids.This soap can obtain from any triglyceride level that is used for the soap manufacturing traditionally, and therefore the carboxylate anion in this soap can be contained 8 to 22 carbon atoms.
Other detergent active compound can be negatively charged ion, nonionic, positively charged ion, zwitter-ion or amphoteric tensio-active agent, and is perhaps known as those of skill in the art, also its mixture can be attached in this prescription.Wherein the anionic detergent active substance comprises that constituting of alkylbenzene sulfonate (LAS) is preferred especially.
Detergent active material is for example formed 5 to 60% of weight by whole stripe shape agent to be that normal amount exists for detergent bar, is preferably 10-50%, more preferably is 12 to 45%.
Produce structural system on the spot and use silicate to finish, it is preferably water glass, has SiO
2: Na
2The O mol ratio more preferably is less than 3 less than 4 type, is most preferably between 3 and 1.
Washing assistant:
Detergent builders used in the prescription is preferably inorganic, and suitable washing assistant comprises such as alkali metal aluminosilicate (zeolite), alkaline carbonate, Tri sodium Phosphate (STPP), tetrasodium pyrophosphate (TSPD), Citrate trianion, sodium nitrilo triacetate (NTA) and these combination.Washing assistant is fit to be used with 0 to 30% total amount.
Inorganic particle:
Inorganic particle is not the neccessary composition of prescription mutually, but can add, especially for the clean synthetics of crust.This particle preferably includes constitution agent and/or water-fast abrasive material mutually.The agent of suitable inorganic particle structure can be selected from particulate zeolite, calcite, rhombspar, feldspar, silica, silicate, different carbonate, supercarbonate, boric acid, vitriol and the polymeric material as the polyethylene.
Most preferred inorganic particle is mixture (as rhombspar), sodium bicarbonate, borax, sodium sulfate/potassium, zeolite, feldspar, talcum, kaolin and the silica of lime carbonate (as calcite), lime carbonate and magnesium.
Calcite, talcum, kaolin, feldspar and rhombspar with and composition thereof especially preferred because its low cost and color.
Other conventional inorganic particle structure agent such as silico-aluminate can produce on the spot, perhaps the type that is easy to obtain can be added.
Other additive:
The additive that can add other, for example one or more water-fast polyose particulate materials as starch or treated starch and Mierocrystalline cellulose.
Supplementary additive:
Conventional ancillary component preferably is selected from enzyme, anti redeposition agent, white dyes, colorant, sanitas and spices, SYNTHETIC OPTICAL WHITNER, SYNTHETIC OPTICAL WHITNER parent, bleaching stibilizer, sequestrant, stain remover (being generally polymkeric substance) and other polymkeric substance can also be added, extremely up to 10 weight %.
Explanation to several unrestricted embodiment is provided here, shows the comparative result of the synthetics that the present invention is obtained.Table 1 in 3 with reference to stripe shape agent the details and the result thereof of this composition have been described.The manufacturing of detergent bar is carried out as described belowly.
Embodiment
Embodiment 1
Make the method for detergent bar:
A. ordinary method:
By the 1.2kg linear alkyl benzene sulphonic acid being placed a Z-blade mixer and making 6kg detergent bar batch of material with 600g yellow soda ash neutralization. generate silico-aluminate on the spot by the reaction of 180g Tai-Ace S 150 and 120g water glass.And the composition that adds other is such as 720g Tri sodium Phosphate (STPP) component, about 3kg filler, water and ancillary component.Make these composition thorough mixing and in addition mold pressing (embodiment 1a) in a conventional way.
B. the inventive method:
By the 1.2kg linear alkyl benzene sulphonic acid being placed a Z-blade mixer and making 6kg detergent bar batch of material with 600g yellow soda ash neutralization.In this stirrer by 30g Tai-Ace S 150,180g alkalimetal silicate and the reaction of 90g calcium chloride and in the active substance back generating structure system that neutralizes fully.And the composition that adds other, such as 720g STPP component, about 3kg filler, water and ancillary component.Make these composition thorough mixing and in addition mold pressing (embodiment 1b) in a conventional way.
Make according to following details for other structural system relatively.In all prescriptions, the entire infrastructure composition maintained and approach 5% of the gross weight of filling a prescription.
Embodiment 1c: by the reaction of 180g water glass and 120g calcium chloride and generate Calucium Silicate powder on the spot.
Embodiment 1d: by 30g Tai-Ace S 150 and 30g alkali metal silicate reactant salt and generate silico-aluminate on the spot and by the reaction of 90g calcium chloride and 150g alkalimetal silicate and the Calucium Silicate powder after generating dosing.
Embodiment 1e: generate the ca aluminosilicate behind the dosing by 30g Tai-Ace S 150,180g alkalimetal silicate and the reaction of 90g calcium chloride.
Embodiment 1f: generate calcium borosilicate on the spot by 30g boric acid, 210g alkalimetal silicate and 72g reacting aluminum sulfate.
Measure different physics and service performance according to follow procedure with the obtained stripe shape agent of aforesaid method, and with the details of prescription and data presentation in table 1.
The mensuration of detergent bar hardness
For certain humidity level, the hardness of detergent bar is the direct indicator of this detergent bar structure quality.Use penetrometer to obtain the hardness of this detergent bar and the estimated value of yielding stress based on the depth of penetration of pin.Run through dark more, then hardness and yielding stress are just more little, and vice versa.Measurement is by allowing one to have the pins of 9 degree cone angles to drop to the flat table curved surface top of this detergent bar carry out for 5 seconds under the fixed weight of 50g.This depth of penetration is come record with mm.
Hydropexis
The hydropexis ability of detergent bar is come quantitative in addition by the activity of measuring water in this detergent bar.This measurement is carried out on the AW Sprint of Switzerland Novasina company model instrument.Make this detergent bar sample balance that grid arranged in the temperature of setting, and extrapolate its relative humidity by the device that shows water activity.Certain humidity level, the ability that this detergent bar of the low more expression of the activity of water keeps water is good more, and therefore the structure in this detergent bar is just good more.
The evaluation method of mashed prod
This mashed prod means when contacting with water, the layer of formed picture ointment on this detergent bar surface.This one deck to this stripe shape agent easily on fabric spreading useful, still, excessive formation mashed prod by the human consumer think the waste (economical and practical inadequately).
The mensuration program
1) planishes this detergent bar with carpenter's plane and remove the unfairness on surface, for example ripple identification pattern etc.
2) the weigh detergent bar (W of this planing
1G).
3) the part bar surface of above planing detergent bar was immersed in the 250ml distilled water 20 minutes.
4) at the end in the pond, took out this detergent bar and some times of drip-dry at 20 minutes.
5) gently scrape the surface that is exposed to water and collect this loose material that adheres to (adhering to mashed prod) with petrochemical industry vessel (Pg) of weighing in advance.Weigh together this vessel and adhere to mashed prod (W
2G) also by weight difference (W
3=W
2-P) find out the weight (W that this adheres to mashed prod
3G).
6) the dissolving loss of measuring this detergent bar by the increase of measuring the weight of burning water in the cup.
Table 1
| Constituent wt.% | Embodiment 1a | Embodiment 1b | Embodiment 1c | Embodiment 1d | Embodiment 1e | Embodiment 1f |
| Na LAS | 20 | 20 | 20 | 20 | 20 | 20 |
| Component * | 18 | 18 | 18 | 18 | 18 | 18 |
| Filler * | 46.3 | 46.3 | 46.3 | 46.3 | 46.3 | 46.3 |
| Constituent is on the spot/quantitatively after the charging | On the spot | On the spot | On the spot | Al-Si on the spot, quantitatively Ca-Si after the charging | Ca-Al-Si after the quantitative charging | On the spot |
| Tai-Ace S 150 | 3 | 0.5 | - | 0.5 | 0.5 | - |
| Alkalimetal silicate | 2 | 3 | 3 | 3.0 | 3 | 3.5 |
| Calcium chloride | 1.5 | 2 | 1.5 | 1.5 | 1.2 | |
| Boric acid | - | - | - | - | - | 0.5 |
| % humidity | It is 10 ± 0.3% that humidity fixes on 10%-actual | |||||
| Ancillary component | To 100 | |||||
| Run through, mm is at 30 ℃ | 1.92 | 1.35 | 1.69 | 1.88 | 2.28 | 1.48 |
| The activity of water | 0.723 | 0.658 | 0.66 | 0.692 | 0.66 | 0.657 |
*Component utilized is yellow soda ash and STPP.
*Used filler is calcite, calcium hydroxide and the china clay washed.
Run through shallow more, hardness is high more.We find from run through measurement, the detergent bar (Ex.1a) that the detergent bar (Ex.1b) that ca aluminosilicate constitutes constitutes than the silico-aluminate on the spot and detergent bar (Ex.1c) of Calucium Silicate powder formation is harder on the spot.And, with the detergent bar (Ex.1e) that only generates silico-aluminate on the spot and quantitatively generate the detergent bar (Ex.1d) of Calucium Silicate powder after the charging and quantitatively generate ca aluminosilicate after the charging relatively, the detergent bar (Ex.1b) that the present invention generates ca aluminosilicate on the spot is harder significantly.This just strengthens the fact that this structure must form on the spot.
The lower lower loss in weight of water activity hint lay up period.Data declaration in the table 1 compares detergent bar of the present invention with the detergent bar (Ex.1a) that traditional aluminosilicate structure is arranged and has lower water activity.This shows that detergent bar of the present invention will lose less water in storage process.
This invention is not limited to the only combination of a metal ion species, i.e. calcium and aluminium.More than a kind of metal ion combination can generate this structure with the water glass reaction.Embodiment 1f shows a kind of such situation.In this case, the salt of boracic, boric acid and calcareous salt, calcium chloride generate the calcium borosilicate structure on the spot with the alkali metal silicate reactant salt.This structure is also improved the hardness of this detergent bar and is reduced its water activity.
Embodiment 2
Use structural system of the present invention to make the stripe shape agent of no china clay
The details of complying with as described in example 1 above prepares 6kg stripe shape agent batch of material.For each situation, important system component is emphasized as follows:
Embodiment 2a: conventional aluminosilicate structure uses 180g Tai-Ace S 150 and 120g alkalimetal silicate.There is 8.3% china clay in this prescription.Other filler is calcite (35%) and calcium hydroxide (3%).
Embodiment 2b: conventional aluminosilicate structure uses 180g Tai-Ace S 150 and 120g alkalimetal silicate.Replace whole china clay (8.3%) with calcite.The total amount of calcite is 43.3% in this prescription.
Embodiment 2c: in this embodiment, structure is finished according to the present invention.Generate the ca aluminosilicate structure with 30g Tai-Ace S 150,180g alkalimetal silicate and 90g calcium chloride.Whole china clay (8.3%) in this prescription are replaced by calcite.The total amount of calcite is 43.3 in this prescription.Table 2 provides the details of this prescription.
Table 2
| Constituent wt% | Embodiment 2a | Embodiment 2b | Embodiment 2c | |
| Na LAS | 20 | 20 | 20 | |
| Component * | 18 | 18 | 18 | |
| Calcite | 35 | 43.3 | 43.3 | |
| Calcium hydroxide | 3 | 3 | 3 | |
| Washing china clay | 8.3 | - | - | |
| Constituent is on the spot/quantitatively after the charging | On the spot | On the spot | On the spot | |
| Tai-Ace S 150 | 3 | 3 | 0.5 | |
| Alkalimetal silicate | 2 | 2 | 3 | |
| Calcium chloride | - | - | 1.5 | |
| % humidity | Fix on 10% (actual is 10 ± 0.3%) | |||
| Ancillary component | To 100 | |||
| The depth of penetration, mm | 50℃ | 3.51 | 5.02 | 2.98 |
| 30℃ | 1.92 | 2.95 | 1.48 | |
| The activity of water | 0.723 | 0.72 | 0.657 | |
*Component utilized is STPP and soda.
In table 2, at first compare the detergent bar that has and do not have china clay (being respectively embodiment 2a and 2b) that silico-aluminate constitutes.Measure indicatedly as running through, the detergent bar of the china clay of not washing (ex.2b) is softer than the detergent bar that china clay is arranged (ex.2a).This confirms that removing the china clay of washing for conventional aluminosilicate structure just makes detergent bar softer.But for ca aluminosilicate structure (embodiment 2c), even this detergent bar is still harder after removing washing china clay, shows that the detergent bar that uses this structure can be made without china clay.In addition, the water activity of stripe shape agent of the present invention is lower.
Embodiment 3
The measurement of adhering to mashed prod
According to previous described program the sample that makes by embodiment 1a and embodiment 1b being carried out mashed prod measures.The result provides in table 3.
Table 3
| Prescription | Adhere to mashed prod, g | The dissolving loss of detergent bar, g |
| The detergent bar that silico-aluminate constitutes, Ex.1a | 2.9 | 1.7 |
| The detergent bar that ca aluminosilicate constitutes, Ex.1b | 2.4 | 1.1 |
From table 3 obviously as seen, with conventional aluminosilicate structure (Ex.1a) relatively, the detergent bar (Ex.1b) that ca aluminosilicate constitutes has and lower adheres to mashed prod and detergent bar dissolves loss.This hints that detergent bar of the present invention has the noticeable mashed prod benefit of human consumer.
Claims (5)
1. detergent bar, it comprises:
(i) be 5% to 60% detergent active material by weight, this detergent active material is soap or non-soap, is selected from straight chain and branch-alkylbenzene sulfonate, sulfonated alkane, secondary alcohol sulfate, primary alcohol sulfate,, sulfonated, sulfated alkyl ether, fatty acyl group sulfonated ester, alkyl carboxylate and these mixture; With
(ii) be 2% to 20% structural system by weight, this structural system is the situ reaction products of two kinds of different polyvalent ions with water glass, and wherein a kind of ion is calcium or magnesium, and another kind then is selected from boron, aluminium, zinc, calcium or magnesium.
2. the detergent bar of claim 1, wherein water glass is SiO
2: Na
2The mol ratio of O is less than 4 type.
3. claim 1 or 2 detergent bar, wherein this bar does not contain any china clay.
4. method of making the detergent bar of claim 1, this method may further comprise the steps:
(i) in the composition that comprises the detergent active material that exists to the small part detergent bar or its acid parent, by making two kinds of different polyvalent metal ions, at this acidity parent fraction or before neutralizing fully, in the N-process and/or after the neutralization, produce structural system on the spot with the water glass reaction;
(ii) step (i) before, in the process and/or add other composition afterwards, this other composition is selected from different detergent active materials, washing assistant, filler and other conventional ingredient; With
(iii) resulting block is converted to the product form of hope.
5. the method for claim 4, wherein structural system generates in the acid parent of the detergent active material back that neutralizes fully.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1073MU2001 | 2001-11-08 | ||
| IN1073/MUM/2001 | 2001-11-08 | ||
| GB0130715A GB0130715D0 (en) | 2001-12-21 | 2001-12-21 | Detergent bar composition and process for its manufacture |
| GB0130715.6 | 2001-12-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1582324A CN1582324A (en) | 2005-02-16 |
| CN1258586C true CN1258586C (en) | 2006-06-07 |
Family
ID=26246897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028220234A Expired - Fee Related CN1258586C (en) | 2001-11-08 | 2002-10-09 | Detergent bar composition and process for its manufacture |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1258586C (en) |
| BR (1) | BR0213750A (en) |
| MY (1) | MY128769A (en) |
| WO (1) | WO2003040283A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116635511A (en) | 2020-12-10 | 2023-08-22 | 联合利华知识产权控股有限公司 | Laundry soap bar compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2099013B (en) * | 1981-05-21 | 1985-03-06 | Unilever Plc | Built detergent bars |
| GB8506684D0 (en) * | 1985-03-14 | 1985-04-17 | Unilever Plc | Laundry bars |
| DE3612701A1 (en) * | 1986-04-15 | 1987-10-22 | Degussa | DETERGENT IN PIECE SHAPE |
| GB2235205A (en) * | 1989-08-10 | 1991-02-27 | Unilever Plc | Detergent laundry bars |
| GB2234982A (en) * | 1989-08-10 | 1991-02-20 | Unilever Plc | Detergent laundry bars |
| GB2256647A (en) * | 1991-06-13 | 1992-12-16 | Unilever Plc | Detergent composition |
| CN1213136C (en) * | 1999-12-08 | 2005-08-03 | 荷兰联合利华有限公司 | Process of preparing detergent bar composition |
| WO2002046341A2 (en) * | 2000-12-05 | 2002-06-13 | Unilever N.V. | Process for manufacture of non-granular solid detergent composition |
-
2002
- 2002-10-09 BR BR0213750-0A patent/BR0213750A/en not_active IP Right Cessation
- 2002-10-09 WO PCT/EP2002/011261 patent/WO2003040283A1/en not_active Application Discontinuation
- 2002-10-09 CN CNB028220234A patent/CN1258586C/en not_active Expired - Fee Related
- 2002-11-06 MY MYPI20024141A patent/MY128769A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1582324A (en) | 2005-02-16 |
| MY128769A (en) | 2007-02-28 |
| BR0213750A (en) | 2004-10-19 |
| WO2003040283A1 (en) | 2003-05-15 |
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