EP1010752A1 - Unique multifunctional product for detergent formulations - Google Patents
Unique multifunctional product for detergent formulations Download PDFInfo
- Publication number
- EP1010752A1 EP1010752A1 EP98931108A EP98931108A EP1010752A1 EP 1010752 A1 EP1010752 A1 EP 1010752A1 EP 98931108 A EP98931108 A EP 98931108A EP 98931108 A EP98931108 A EP 98931108A EP 1010752 A1 EP1010752 A1 EP 1010752A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- product
- detergent
- detergent formulations
- raw materials
- single product
- 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.)
- Withdrawn
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 238000009472 formulation Methods 0.000 title claims abstract description 60
- 239000000047 product Substances 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 14
- 241001625808 Trona Species 0.000 claims abstract description 11
- 239000004576 sand Substances 0.000 claims abstract description 11
- 239000011435 rock Substances 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000013067 intermediate product Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010755 mineral Nutrition 0.000 claims description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012263 liquid product Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 11
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Images
Classifications
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/16—Phosphates including polyphosphates
Definitions
- This invention refers to a multifunctional single product for detergent formulations, and more particularly, to a product in the form of a powder or a glass, which is water soluble and acts as builder, conditioner, filler and carrier, among others, in the detergent and in the process for its manufacture.
- phosphorus oxide P 2 O 5
- sodium oxide Na 2 O
- silica SiO 2
- B 2 O 3 boron oxide
- These oxides are normally provided through a plurality of raw materials or chemical compounds, such as the sodium carbonate (Na 2 CO 3 ), sodium tripolyphosphate (Na 5 P 3 O 10 ), sodium sulfate (Na 2 SO 4 ), sodium silicate (xNa 2 O ⁇ ySiO 2 ) and sodium borate (Na 2 B 4 O 7 ).
- sodium carbonate Na 2 CO 3
- sodium tripolyphosphate Na 5 P 3 O 10
- sodium sulfate Na 2 SO 4
- sodium silicate xNa 2 O ⁇ ySiO 2
- sodium borate Na 2 B 4 O 7
- each detergent producer has its own formulations, but each producer normally buys and uses the above-mentioned typical chemical compounds as raw materials.
- each of such compounds performs a task, acting as a builder, as a conditioner, as a filler, as a carrier, as a neutralizing agent, etc. in the detergent and /or in the process for its manufacture.
- the sodium tripolyphosphate a raw material normally used in the detergent formulation as a source of phosphorus oxide (P 2 O 5 ), is made by reacting phosphoric acid with sodium carbonate; that in turn, the phosphoric acid is obtained from the reaction of the grounded phosphoric rock with sulfuric acid, which is filtered for impurity elimination which is not but silica which is also present in the detergent formulation; and that the sodium carbonate is normally obtained by a process for the benefitiation of the trona ore by impurity elimination which is not but silica which is also present in the detergent formulations.
- the impurity compounds are also materials present in the detergent formulations, and that the process for their elimination add a cost to the raw materials and consequently to the final detergent, then the mineral treatment to obtain such raw materials becomes unnecessary and the phosphoric rock or at least the phosphoric acid can be used, through just a partial treatment (such as acid or alkaline attack, as well as grounding, sieving and screening), to produce a product which would be used as a source of P 2 O 5 and as a partial source of SiO 2 in the detergent formulations.
- a partial treatment such as acid or alkaline attack, as well as grounding, sieving and screening
- the Na 2 O is provided through the sodium carbonate obtained from the treatment of trona mineral by a process including grounding, diluting, filtering to eliminate compounds considered as impurities (which are compounds also used in the detergent formulations) and crystallizing, to obtain the sodium carbonate.
- trona mineral could be used directly, through a simple grounding step, at more reduced costs, to prepare a single product which would be adjusted to the detergent formulation needs.
- the SiO 2 is provided through the sodium silicate which is obtained from reacting silica sand and sodium carbonate in a furnace.
- the multifunctional product developed by applicants will provide the silica that the detergent formulation needs.
- the detergent producer will have not the need to buy 5 or 8 different raw materials for its formulation, but a single product which is less expensive because it will not include the costs of the purifying processes incorporated in each raw material and because such a product involves just one process, instead of each process to produce each of the actual raw materials.
- This product will provide the oxide needs for the detergent formulation and for its manufacturing process and will perform the essential roles or functions such as builder, conditioner, filler, carrier, neutralizing agent, etc. in detergent formulations and in its manufacturing process.
- This product can also be used in the processes for producing detergents, instead of all the raw materials used in the conventional processes, to achieve each of the roles or functions as builder, carrier, filler, among others.
- the obtained product is soluble in water and it will perform the essential roles or functions such as builder, conditioner, filler, carrier, etc. in detergent formulations and in its manufacturing process and results less expensive than the raw materials normally used.
- the detergent producers changed their process technology to produce detergents in the tower process and in the agglomerate process. In both cases they needed almost the same type of raw materials, however they needed solid and liquid raw materials such as sodium tripolyphosphate and sodium silicate.
- solid and liquid raw materials such as sodium tripolyphosphate and sodium silicate.
- the detergent producer does not have to pay for multiple raw material handling and transportation, nor to pay for transporting some unneeded volatile or gaseous components such as the CO 2 , that are present in the raw materials used such as in the sodium carbonate.
- the reacting step is carried out either, at a temperature under the melting point of the mixture, to produce a powder, or at a reacting and melting temperature of the mixture, to provide a glass.
- the process comprising to dissolve the powder or the glass product in a solvent, to produce a liquid product including most of the typical oxides normally included in the detergent formulations.
- a final annealing step for the product can be introduced in the process.
- the single reacted product, in accordance with the present invention include the essential oxides, such as phosphorus oxide (P 2 O 5 ), sodium oxide (Na 2 O), silica (SiO 2 ), balanced in accordance with the specific detergent formulations, which is water soluble and performs as builder, conditioner, filter, carrier and neutralizing agent, in the product and in the process for the manufacturing of the detergent.
- the essential oxides such as phosphorus oxide (P 2 O 5 ), sodium oxide (Na 2 O), silica (SiO 2 )
- the specific detergent formulations which is water soluble and performs as builder, conditioner, filter, carrier and neutralizing agent, in the product and in the process for the manufacturing of the detergent.
- the final oxide content of the product of the present invention will depend on the type and oxide content of the detergent formulation, which detergent producers normally keep secret.
- This batch 5 was reacted in a rotary kiln K at a temperature of about 800°C and then the reacted batch 6 was fed to a furnace F to melt the reacted batch 6 at a temperature of about 1200°C, to produce one ton of a glass product 7.
- This batch 5 was reacted in a rotary kiln K at a temperature of about 800°C and then the reacted batch 6 was fed to a furnace F to melt the batch 6 at a temperature of about 1200°C, to produce one ton of a glass product 7.
- the sodium carbonate from the feeder 1a and the silica sand from the feeder 2 were feed to a mixer M to homogenize the primary raw materials; the mixture 3 was then introduced into an agglomerator A to which the phosphoric acid 4a was added to agglomerate these raw materials to produce a batch 5 in the following ratio 1P 2 O 5 : 4Na 2 O : 4 SiO 2 .
- This batch 5 was directly reacted in the furnace F to melt the batch 5 at a temperature of about 1200°C, to produce one ton of a glass product 7.
- sodium sulfate from a feeder 8 was directly added, in an amount of 10% by weight, to the mixer M containing the natural or partially treated raw materials of the Examples 1 to 3, reacted in the kiln K and melted in the furnace F in accordance with Examples 1 and 2, or directly reacted and melted in the furnace F in accordance with the Example 3, at the same temperature than the above examples, to produce a glass product 7a.
- the glass product 7 from Examples 1 to 3 or 7a from the Example 4 was fed to mill ML, milled therein and the milled mixture 9 was fed to a mixer M2 in which an additional amount of sodium sulfate from a feeder 8a was added to milled mixture 9, in a double amount of the weight of the product 7 or 7a, to obtain the product 7b.
- Grounded trona ore from feeder 1 and silica sand from feeder 2 were feed to the mixer M to homogenize the primary raw materials; the mixture 3 was then introduced into the agglomerator A in which treated (acid attacked) phosphoric rock from feeder 4 was added to agglomerate these raw materials to produce a batch 5 in the following ratio 1P 2 O 5 : 4Na 2 O : 4 SiO 2 .
- This batch 5 was directly reacted in the rotary kiln K at a temperature of about 700°C to produce a powder product 7c.
- the product 7 or 7a of Examples 1 to 4, or 7c of the Example 6 was dissolved in water, at a temperature of 90°C in a dissolver D, to produce a liquid product 7d having a concentration of 33% of the total product.
Landscapes
- 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)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89012197A | 1997-07-09 | 1997-07-09 | |
| US890121 | 1997-07-09 | ||
| PCT/MX1998/000023 WO1999002643A1 (es) | 1997-07-09 | 1998-06-17 | Un solo producto multifunctional para formulaciones de detergente |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1010752A1 true EP1010752A1 (en) | 2000-06-21 |
Family
ID=25396286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98931108A Withdrawn EP1010752A1 (en) | 1997-07-09 | 1998-06-17 | Unique multifunctional product for detergent formulations |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP1010752A1 (xx) |
| JP (1) | JPH11106787A (xx) |
| CN (1) | CN1262704A (xx) |
| AR (1) | AR013187A1 (xx) |
| BR (1) | BR9810987A (xx) |
| CA (1) | CA2295702A1 (xx) |
| CO (1) | CO5031341A1 (xx) |
| EG (1) | EG21669A (xx) |
| HU (1) | HUP9801520A2 (xx) |
| IL (1) | IL125269A (xx) |
| MA (1) | MA24602A1 (xx) |
| PE (1) | PE95199A1 (xx) |
| TR (1) | TR199801307A3 (xx) |
| WO (1) | WO1999002643A1 (xx) |
| ZA (1) | ZA985929B (xx) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004020033A1 (de) * | 2004-04-21 | 2005-11-10 | Henkel Kgaa | Verbrauchsanzeiger für maschinelle Geschirrspülmittel |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000009641A1 (en) * | 1998-08-17 | 2000-02-24 | The Procter & Gamble Company | Multifunctional detergent materials |
| WO2001092448A2 (es) * | 2000-05-31 | 2001-12-06 | Vitro Corporativo, S.A. De C.V. | Composicion de oxidos soluble en agua, para formulaciones de detergente |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3270156B2 (ja) * | 1992-11-12 | 2002-04-02 | 花王株式会社 | 無機ビルダー |
| US5393446A (en) * | 1992-12-16 | 1995-02-28 | Eco Japan Co., Ltd. | Process for preparing detergent composition containing sodium and potassium oxides |
| JPH0859225A (ja) * | 1994-08-18 | 1996-03-05 | Tokuyama Corp | 非晶質珪酸カリウム粉末及びその製造方法 |
| JPH08143309A (ja) * | 1994-11-17 | 1996-06-04 | Tokuyama Corp | 非晶質珪酸ナトリウム・炭酸ナトリウム複合体の製造方法 |
-
1998
- 1998-06-17 EP EP98931108A patent/EP1010752A1/en not_active Withdrawn
- 1998-06-17 BR BR9810987-1A patent/BR9810987A/pt not_active Application Discontinuation
- 1998-06-17 CA CA002295702A patent/CA2295702A1/en not_active Abandoned
- 1998-06-17 WO PCT/MX1998/000023 patent/WO1999002643A1/es not_active Application Discontinuation
- 1998-06-17 CN CN98807065A patent/CN1262704A/zh active Pending
- 1998-07-04 EG EG78898A patent/EG21669A/xx active
- 1998-07-06 ZA ZA9805929A patent/ZA985929B/xx unknown
- 1998-07-06 MA MA25160A patent/MA24602A1/fr unknown
- 1998-07-07 TR TR1998/01307A patent/TR199801307A3/tr unknown
- 1998-07-07 AR ARP980103292A patent/AR013187A1/es unknown
- 1998-07-08 JP JP10207096A patent/JPH11106787A/ja active Pending
- 1998-07-08 IL IL12526998A patent/IL125269A/en not_active IP Right Cessation
- 1998-07-08 CO CO98038767A patent/CO5031341A1/es unknown
- 1998-07-08 HU HU9801520A patent/HUP9801520A2/hu unknown
- 1998-07-09 PE PE1998000609A patent/PE95199A1/es not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9902643A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004020033A1 (de) * | 2004-04-21 | 2005-11-10 | Henkel Kgaa | Verbrauchsanzeiger für maschinelle Geschirrspülmittel |
Also Published As
| Publication number | Publication date |
|---|---|
| EG21669A (en) | 2002-02-27 |
| WO1999002643A1 (es) | 1999-01-21 |
| JPH11106787A (ja) | 1999-04-20 |
| HU9801520D0 (en) | 1998-08-28 |
| CA2295702A1 (en) | 1999-01-21 |
| TR199801307A2 (xx) | 1999-10-21 |
| ZA985929B (en) | 1999-08-13 |
| PE95199A1 (es) | 1999-10-14 |
| TR199801307A3 (tr) | 1999-10-21 |
| CN1262704A (zh) | 2000-08-09 |
| IL125269A (en) | 2001-08-08 |
| CO5031341A1 (es) | 2001-04-27 |
| MA24602A1 (fr) | 1999-04-01 |
| AR013187A1 (es) | 2000-12-13 |
| BR9810987A (pt) | 2000-08-08 |
| HUP9801520A2 (hu) | 1999-09-28 |
| IL125269A0 (en) | 1999-03-12 |
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