AU6410690A - Liquid detergents and cleaning solutions: builder therefor - Google Patents
Liquid detergents and cleaning solutions: builder thereforInfo
- Publication number
- AU6410690A AU6410690A AU64106/90A AU6410690A AU6410690A AU 6410690 A AU6410690 A AU 6410690A AU 64106/90 A AU64106/90 A AU 64106/90A AU 6410690 A AU6410690 A AU 6410690A AU 6410690 A AU6410690 A AU 6410690A
- Authority
- AU
- Australia
- Prior art keywords
- detergent
- silicate
- sio
- silicates
- detergents
- 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.)
- Abandoned
Links
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/08—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
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)
Description
LIQUID DETERGENTS AND CLEANING SOLUTIONS:
BUILDER THEREFOR
Background of the Invention
This invention relates to cleaning solutions, especially liquid laundry detergents. In particular, the invention involves quaternary ammonium silicates as builders or co-builders for liquid cleaners and laundry detergents.
Formulation problems primarily associated with laundry detergents have changed over the years as a result of the development and availability of raw materials, government regulations, and public taste and acceptance of such products. One of the most important problems associated with laundering and laundry products is water hardness and its geographic variability. Hard water contains calcium and magnesium ions that inhibit the action of most surface active agents included in the formulation to perform the greatest portion of the cleaning job. The usual way of combating hard water is to include a builder in the formulation. Such builders function by reducing or eliminating the activity of calcium and/or magnesium ions but do not interfere with detersive action if said ions are not present.
Initially these builders were precipitants- -they reduced the activity of calcium and magnesium ions by precipitation from the washing bath. The activity of the hard water ions was effectively reduced, but the precipitated salts deposited onto fabrics, turning white fabrics grayish. The complex phosphates essentially displaced the earlier builders since they sequester the calcium and magnesium and maintain the resulting inactive complex in solution so that deposits do not form on clothes.
Phosphates remained the builder of choice for many years, since they provided powder detergent with excellent cleaning properties. Liquid detergents that were built with phosphates were developed as taught in U.S. Patents 3,001,945; 3,066,104 and 3,208,947. These products could not compete with phosphate built powders.
Recently many factors have changed washing practices and detergent formulations. These include new fabrics, new raw materials, higher energy costs, and government regulations of phosphate discharge into the environment. In this changing marketplace, liquid detergents have been competing successfully with detergent powders.
The compositions of these liquid detergents are limited, because producing relatively stable systems with a number of components has proved difficult. In general, these systems do not contain builders, or they contain expensive organic sequestering agents such as sodium citrate. In addition, other ingredients known as hydrotropes may be required to stabilize the liquids. These combinations are expensive and increase to some degree the BOD load on water treatment facilities.
In addition, the incorporation of silicate for corrosion control, for sequestration of magnesium ions, and as a source of alkalinity has been very difficult because of stability problems. U.S. Patents 3,935,192 and 4,388,205 teach the inclusion of silicates in liquid compositions of either very high pH or very complex, expensive composition.
It is an object of this invention to provide organic silicates that have not previously been used in detergents and that provide stable liquid detergents and cleaning solutions. It is another object of this invention to provide combinations of silicates that provide competitive building and cleaning power for detergents. Further objectives of this invention are to provide liquid detergents and cleaning solutions that utilize these silicates in less complex formulations and that provide corrosion protection.
Summary of the Invention
We have found that certain quaternary ammonium silicates have structures that differ from alkali metal silicates sufficiently to allow formulation of less complex liquid detergents and cleaning solutions. These silicates that contain 0.8 to 5.0 moles of SiO2 per mole of Q2O (Q = quaternary ammonium ion) can be formulated with combinations of surfactants and other detergent ingredients without the need for expensive hydrotropes. If appropriate hydrotropes are included in the composition, the ingredients and amounts of ingredients can vary more widely. For example, a higher level of silicate can be used in the detergent. The silicates that provide such stable liquid detergents have compositions wherein Q has a molecular weight of less than 240. These silicates provide builder properties by enhancing the performance of the surfactants. They can be formulated with organic sequestering agents as co-builders. A combination of sodium and/or potassium silicate and the quaternary ammonium silicate also provides excellent detergent properties.
The liquid detergents or cleaners of our invention containing our limited number quaternary ammonium silicates use water as the solvent and/or continuous phase. Some undissolved materials may be suspended in the liquid, especially if the material is thickened. Non-aqueous liquids can also be used as the solvent and/or continuous phase. Liquid surfactants can be used, and our selected quaternary ammonium silicates are compatible with such systems. The Invention
The organic ammonium silicates useful in detergents and cleaners, especially liquid detergents and/or cleaning solutions, are of limited composition when considering the class of such organic silicates. U.S. Patents 3,239,521; 3,301,853; 3,346,334 and 3,383,386 disclose a broad range of organic ammonium silicates. These silicates have not been formulated into stable liquid detergents and/or cleaning
solutions. Organic ammonium silicates that do form stable liquid detergents that are effective cleaning materials should contain 0.8 to 5.0 moles of SiO2 for each mole of O-O. The composition of Q is important in providing the desired silicate. Its structure is as follows:
Q = Rn R'n' (CH2CH2OH)4-(n + n')N+
When R and R' are methyl or ethyl, n + n' can be 0 to 4. If R is propyl, isopropyl or butyl n is 1 and n' must be 0. In general, the molecular weight of Q is less than about 240. The materials are available, as the hydroxides, as articles of commerce, or can be prepared by numerous well known syntheses such as the ethoxylation of amines. We do not believe that Q2O exists in nature, but have adopted the convention used in the silicate industry of expressing the silicate compositions as oxides.
The silicate is formed by dissolving a source of silica in the quaternary ammonium hydroxide. In general, nearly pure silica sources with associated water that dissolve in the hydroxide and equilibrate quickly are the most desirable. Silica gels made by neutralizing or partly neutralizing sodium or potassium silicate solution are very useful. Sodium or potassium silicates that have been partially or completely de-alkalized by methods such as ion exchange are also useful. We prefer to use a silica gel.
The quaternary ammonium silicates that conform to these compositional requirements provide stable cleaning solutions or liquid detergents when combined with surfactants and other detergent ingredients. We consider a detergent stable if it passes all the tests accepted by the manufacturers of such products. The detergent must be stable under storage at room temperature for one year. It must be stable for one month at 50°C or two months at 40°C and for a minimum of 4 months at 1.7 to 4.4°C. The liquid detergent must also be stable for seven freeze/thaw cycles. Each cycle involves 24 hours at -15°C and 24 hours at room temperature. Stability is evident if there is no phase separation, precipitation or haze formation.
We have found that sodium and potassium silicate solutions do not pass these tests, and that quaternary ammonium silicates that do not have the compositions described hereinbefore do not form stable liquid detergents or components thereof. In addition, we have found that certain levels of SiO2 in the detergent are required for stability when hydrotropes are not included in the formulation. Essentially SiO2 levels of 2.0 to 4.5% by weight provide the most stable liquids. At SiO2 levels less than about 2.0% the detergents failed at least one test. At SiO2 levels of more than about 4.5% the detergent is unstable. If the liquid detergent does contain a hydrotrope to provide additional stability, SiO2 levels up to about 10% can be stable.
The quaternary ammonium silicates of our invention provide builder properties in that they enhance the cleaning surfactants in water that contains ions of calcium and magnesium. The silicates of our invention provide such enhancement even though they have not been found to sequester calcium and/or magnesium ions. Indeed, the quaternary ammonium silicates do not appear to reduce the activity of calcium or magnesium ions in solutions in any way. Despite this lack of sequestering power, combinations of nonionic and anionic surfactants with the quaternary ammonium silicate provide cleaning that is competitive with a combination of the same surfactant system and sodium citrate, a known sequestrant. We therefore define "builder" as, "any materi al that provides enhancement of surfactant performance, " and as such, we consider quaternary ammonium silicates to be builders.
Combinations of the quaternary ammonium silicate and other materials that do reduce the activity of hard water ions such as calcium and magnesium in solution can be added to liquid detergents with advantage. Any material that can reduce these activities, and can be made stable with the surfactants of choice, can be used. Since reduced amounts of such co-builders can be used, some materials previously thought to be unsuitable because of stability problems at effective levels can be used. Inorganic phosphates that are
stable along with organic sequestering agents provide desirable combinations. Especially useful are the various salts of ethylinediaminetetroacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, citric acid, tartrate succinates and polyacetyl carboxylates. Aluminosilicate ion exchange materials are also useful when they are maintained in suspension.
The surfactants useful with the quaternary ammonium silicate of our invention are any that form stable solutions upon combination with our quaternary ammonium silicate, remain stable in storage, and provide the desired cleaning level. We have found nonionic, anionic and combinations thereof to be useful. Zwitterionic and cationic surfactants can be included. Useful nonionic surfactants can be produced by condensing an alkylene oxide such as ethylene oxide with aliphatic or alkyl aromatic compounds. The important property is to balance the hydrophilic and hydrophobic properties to provide stability and cleaning. The useful anionic surfactants include linear straight chain alkyl benzene sulfonates which are often called LAS materials, ether sulfates and alkyl benzene sulfonates that may have branched carbon chains.
The quaternary ammonium silicates of our invention also provide corrosion resistance that has not been available with most liquid detergents previously. Bleach stability is also enhanced by the inclusion of our silicates in such detergents. The relatively simple liquid detergent formulations that include our quaternary ammonium silicate can have lower pH values and allow the use of enzymes that had not been possible in the prior art. Essentially, the use of the quaternary ammonium silicate of our invention allows full formulation of a heavy duty liquid laundry detergent that had not been possible previously.
The liquid detergents containing the quaternary ammonium silicate of our invention are about equal in laundering performance to commercially marketed liquid detergents.
Several of these quaternary ammonium silicates crystallize to form solids at specific mole ratios. These
materials can be used as components of powdered or granular detergents that are dry blended or agglomerated.
Examples
The following examples illustrate certain embodiments of our invention. These examples are not provided to establish the scope of the invention, which is described in the disclosure and recited in the claims. The proportions are in parts by weight (pbw), percent by weight (% wt/wt) or parts per million (ppm) unless otherwise indicated.
The quaternary ammonium silicates used in the following examples were prepared by mixing silica hydrogel (34% SiO2) with the various quaternary ammonium hydroxide solutions at room temperature. The silica gel dissolved to form water clear solutions. The compositions of these silicate solutions were 2 to 8 moles of SiO2 for each mole of Q2O. They contained about 10 to 17% SiO2.
The stability tests were carried out by preparing a skeleton detergent formulation of the components which are most difficult to maintain in a stable liquid. We define a stable liquid for cleaners and detergents as one that provides a clear solution upon synthesis and is stable (does not exhibit phase separation, precipitation or haze) for at least:
1 year at room temperature (1)
1 month at 50°C or 2 months at 40°C (2)
3 months at 3.0 1.5°C (3)
7 freeze/thaw cycles of 24 hours at (4)
-15°C and 24 hours at room temperature
Our skeletal detergent formulation comprises:
Anionic surfactant (linear alkyl sulfonate) 16.5%
Nonionic surfactant (Neodol 25-7 from Shell) 7.5%
Quaternary ammonium silicate (or sufficient ~20.0% to provide the desired level of SiO2)
Water Balance to 100 . 0%
Example 1
Detergents formulated with various ratios of tetramethylammonium silicate were tested for stability. The results are as follows:
Table 1
Stability
(1) (2) (3) (4)
Mole Ratio SiO2 as designated (SiO2/Q2O) (%) hereinbefore
4.0 1.50 (1) (2) (3)
4.0 2.00 (2)
4.0 2.98 Pass
4.0 4.77 (4)
3.3 3.00 Pass
Pass means that all four stability requirements were met. These results indicate that detergents formulated with [(CH3)-N]2O silicate provide stability at about 3%
SiO2.
Example 2
Detergents formulated with trimethylethanol-ammonium silicate, methyltriethanol-ammonium silicate and dimethyldiethyl-ammonium silicate were tested for stability with the following results:
Table 2
Quaternary Mole Ratio SiO2 Stability Ammonium Ion (SiO2/Q2O) (%) (1) (2) (3) (4)
(CH3)3(CH2CH2OH)N+ 4 1.50 (1) (2)
(CH3)3(CH2CH2OH)N+ 4 3.30 Pass
CH3(CH2CH2OH)3N+ 4 1.25 (1) (2)
CH3(CH2CH2OH)3N+ 4 2.00 Pass
CH3(CH2CH2OH)3N+ 4 4.00 (4)
(CH3)2(CH2CH3)2N+ 4 3.30 Pass
Example 3
Detergents formulated with dimethyldiethanol-, trimethylethyl- and methyltriethyl-ammonium silicate and sodium silicates were tested for stability with the following results:
Table 3
Quaternary Mole Ratio
Ammonium Ion (SiO2/Q2O SiO2 Stability or Sodium or Na2O) (%) (1) (2) (3) (4)
(CH3)2(CH2CH2OH)2N+ 4.00 1.5 (2)
(CH3)2(CH2CH2OH)2N+ 4.00 3.3 (4)
(CH3)3(CH2CH2)N+ 4.00 3.3 (4)
Na+ 2.75 1.5 (2) (3) (4)
Na+ 3.30 1.5 (1) (2) (3) (4)
These results indicate that silicates that do not have structures conforming with that described hereinbefore do not form stable detergents under the conditions tested.
Example 4
Detergents were formulated with tetramethylammonium silicate solution and sodium or potassium silicate solution. The results are as follows:
Table 4
Tetramethyl
ammonium Sodium Mole Ratio
Silicate Silicate (SiO2/Q2O SiO2 Stability
(%) (%) + Na2O (%) (1) (2) (3) (4)
15.1 1.6 3.88 2.98 Pass
12.4 3.1 3.72 2.98 Pass
9.8 4.7 3.69 2.98 (2) (4)
7.1 6.3 3.59 2.98 (2) (3) (4)
Tetramethyl
ammonium Potassium Mole Ratio
Silicate Silicate (SiO2/Q2O SiO2 Stability
(%) <%) + K2O (%) (1) (2) (3) (4)
15.1 2.1 4.00 2.98 Pass
12.4 4.3 4.00 2.98 (3)
9.8 6.4 4.00 2.98 (3) (4)
7.1 8.6 4.00 2.98 (2) (3) (4)
These results indicate that some mixtures of quaternary ammonium silicates and alkali metal silicates provide stable liquids, but that if the proportion of inorganic alkali metal is too high instability results.
Example 5
Several detergents formulated with silicates of our invention and a commercial product were tested for laundering efficiency using a Terg-o-tometer. The conditions were as follows.
1. Hardness levels of 150 and 90 ppm were used for washing and rinsing baths.
2. Washing and rinsing were carried out at 105°F.
3. Three types of cloth were used: cotton, polyester and a blend of cotton and polyester. These had standard soils of clay and dust sebum. Clean cloths were used to test redeposition.
4. One and one-half grams of each detergent were used in 1 liter of water for 15 swatches of cloth (2 swatches each of 3 types of cloth and 2 types of soil with 1 clean swatch of each type of cloth).
5. Washing time was 10 minutes and rinsing time was 5 minutes.
6. The cloth swatches were ironed on removal from the rinse bath while being protected from contamination. They were allowed to dry overnight while being protected from contamination.
7. Reflectance numbers for the front and back of each swatch of cloth (washed and unwashed) were obtained using the tristimulus L. scale of a Hunter colorimeter.
The results, expressed as the average of the changes in reflectance
for identical soil-fabric combinations, are summarized in Table 5. These results indicate that liquid commercial detergents wherein the builder sodium citrate has been omitted and a quaternary ammonium silicate of our invention substituted provide satisfactory cleaning when compared to said commercial detergent.
Example 6
The corrosion protection afforded by a tetramethyl-ammonium silicate was tested as follows. Aluminum coupons were submerged in 1% NaOH at room temperature. Gassing developed in a short period of time. Then the silicate of our invention that contained 3.9 moles of SiO2 per mole of
Q2O was added slowly until gassing stopped. The amount of silicate required provided 2.7% SiO2 which is in the range of silica required to provide stable liquid formulations.
Example 7
The laundering efficiency of various surfactants with the silicates of our invention were tested using a Terg-o-tometer as described in Example 5. The hardness level was 90 ppm. The level of surfactants used was 0.0393% of the washing bath. The tetramethyl ammonium silicate (4SiO2/Q2O) was added at 0.026% of the washing. bath. The results for a nonionic surfactant (octyl phenoxy polyethoxy ethanol) are summarized in Table 6. These results show that the addition of the silicate of our invention to the nonionic surfactant provides improved cleaning in most categories. If an antiredisposition agent were added to this formulation, the improvement provided by the quaternary ammonium silicate would be even greater.
The results for an anionic surfactant (C 12-C15-linear primary alcohol ethoxy sulfate ammonium salt) are summarized in Table 7. These results indicate that the addition of the silicate of our invention to the anionic surfactant provides improved cleaning in most categories. If an antiredisposition agent were added to this combination, the improvement provided by the quaternary ammonium silicate would be even greater.
Example 8
The laundering efficiency of another nonionic surfactant with the silicate of our invention and Zeolite A or sodium citrate was tested with a Terg-o-tometer as described in Example 7. The zeolite or citrate was present at levels of .006% of the washing bath. The surfactant was a C12-C15 linear primary alcohol ethoxylate, and the results are summarized in Table 8. These results indicate that the combination of the silicate of our invention and a small amount of a sequestrant provides considerably improved cleaning.
Example 9
The laundering efficiency of linear alkylsulfonate (LAS), an anionic surfactant/ with the silicate of our invention and Zeolite A was tested using a Terg-o-tometer as described in Example 8. The results are summarized in Table 9. These results indicate improved performance of a detergent that would contain both the silicate of our invention and Zeolite A.
Claims (13)
1. A composition useful as an ingredient in cleaning and detergent solutions comprising an organic ammonium silicate that contains 0.8 to 5.0 moles of SiO2 for each mole of Q2O wherein:
Q = Rn R'n' (CH2CH2OH)4-(n + n')N+
R and R' are methyl or ethyl, n + n' is 0 to 4, and Q has a molecular weight of less than 240.
2. A composition useful as an ingredient in cleaning and detergent solutions comprising an organic ammonium silicate that contains 0.8 to 5.0 moles of SiO2 for each mole of Q2O wherein:
Q = Rn R'n' (CH2CH2OH)4-(n + n')N+
R is propyl, isopropyl or butyl, n is 1 and n' is 0, and Q has a molecular weight of less than 240.
3. A detergent or cleaning solution that comprises a surfactant and an organic ammonium silicate that contains 0.8 to 5.0 moles of SiO2 for each mole of Q2O wherein:
Q = Rn R'n' (CH2CH2OH)4-(n + n') N+
R and R' are methyl or ethyl, n + n' is 0 to 4, and Q has a molecular weight of less than 240.
4. The detergent or cleaning solution of claim 3 wherein the organic ammonium silicate provides about 2.0 to
4.5% by weight of SiO2.
5. The detergent or cleaning solution of claim 3 wherein the surfactant is anionic, nonionic or a mixture thereof.
6 The detergent or cleaning solution of claim 4 wherein the surfactant is anionic,. nonionic or a mixture thereof.
7. A detergent or cleaning solution that comprises surfactant, a sodium or potassium silicate and an organic ammonium silicate that contains 0.8 to 5.0 moles of SiO2 for each of mole of Q2O wherein:
Q = Rn R'n' (CH2CH2OH)4-(n + n')N+
R and R' are methyl or ethyl, n + n' is 0 to 4, and Q has a molecular weight of less than 240.
8. The detergent or cleaning solution of claim 7 wherein the surfactant is anionic, nonionic or a mixture thereof.
9. The detergent or cleaning solution of claim 7 wherein the organic ammonium silicate provides about 2.0 to 4.5% by weight of SiO2.
10. A detergent or cleaning solution that comprises a surfactant, a hydrotrope and an organic ammonium silicate that contains 0.8 to 5.0 moles of SiO2 for each mole of of Q2O wherein:
Q = Rn R'n' (CH2CH2OH)4-(n + n')N+
R is propyl, isopropyl or butyl, n is 1, n' is O, and Q has a molecular weight of less than 240.
11. The detergent or cleaning solution of claim 10 wherein the organic ammonium silicate provides about 2.0 to 10% by weight of SiO2.
12. The detergent or cleaning solution of claim 10 wherein the surfactant is anionic, nonionic or a mixture thereof.
13. The detergent or cleaning solution of claim 11 wherein the surfactant is anionic, nonionic or a mixture thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37274889A | 1989-06-28 | 1989-06-28 | |
| US372748 | 1989-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU6410690A true AU6410690A (en) | 1991-01-17 |
Family
ID=23469476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU64106/90A Abandoned AU6410690A (en) | 1989-06-28 | 1990-06-26 | Liquid detergents and cleaning solutions: builder therefor |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0479923A4 (en) |
| JP (1) | JPH04506680A (en) |
| AU (1) | AU6410690A (en) |
| BR (1) | BR9007480A (en) |
| DD (1) | DD300446A5 (en) |
| IE (1) | IE902318A1 (en) |
| NZ (1) | NZ234247A (en) |
| WO (1) | WO1991000330A2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3239521A (en) * | 1961-08-15 | 1966-03-08 | Philadelphia Quartz Co | Amorphous quaternary ammonium silicates |
| SU1470824A1 (en) * | 1986-04-07 | 1989-04-07 | Ленинградское производственное объединение искусственных кож "Пролетарский труд" | Composition for treating pile of polyamide fibre |
| DE3719467A1 (en) * | 1987-06-11 | 1988-12-29 | Hoechst Ag | ORGANICALLY SUBSTITUTED AMMONIUM SILICATES AND METHOD FOR THE PRODUCTION THEREOF |
-
1990
- 1990-06-26 AU AU64106/90A patent/AU6410690A/en not_active Abandoned
- 1990-06-26 EP EP19900913912 patent/EP0479923A4/en not_active Withdrawn
- 1990-06-26 NZ NZ23424790A patent/NZ234247A/en unknown
- 1990-06-26 JP JP51296690A patent/JPH04506680A/en active Pending
- 1990-06-26 WO PCT/US1990/003627 patent/WO1991000330A2/en not_active Application Discontinuation
- 1990-06-26 BR BR909007480A patent/BR9007480A/en not_active Application Discontinuation
- 1990-06-27 IE IE231890A patent/IE902318A1/en unknown
- 1990-06-28 DD DD34226390A patent/DD300446A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9007480A (en) | 1992-06-16 |
| EP0479923A1 (en) | 1992-04-15 |
| EP0479923A4 (en) | 1992-11-25 |
| NZ234247A (en) | 1992-11-25 |
| WO1991000330A3 (en) | 1991-02-21 |
| WO1991000330A2 (en) | 1991-01-10 |
| JPH04506680A (en) | 1992-11-19 |
| IE902318L (en) | 1990-12-28 |
| IE902318A1 (en) | 1991-01-16 |
| DD300446A5 (en) | 1992-06-11 |
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