GB2261218A - Biodegradable sequestrants for detergent compositions - Google Patents
Biodegradable sequestrants for detergent compositions Download PDFInfo
- Publication number
- GB2261218A GB2261218A GB9123402A GB9123402A GB2261218A GB 2261218 A GB2261218 A GB 2261218A GB 9123402 A GB9123402 A GB 9123402A GB 9123402 A GB9123402 A GB 9123402A GB 2261218 A GB2261218 A GB 2261218A
- Authority
- GB
- United Kingdom
- Prior art keywords
- formula
- acid
- composition according
- sequestrants
- sodium
- 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- Withdrawn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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
-
- 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
- C11D3/33—Amino carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
Abstract
Detergent compositions for domestic use or for industrial use, are characterised in that they comprise at least one biodegradable sequestrant of formula (I> <IMAGE> in which: - n is from 1 to 6, - the symbols M1, M2, M3, M4 and M5, identical or different, represent a hydrogen atom, an alkali metal, an ammonium group -NH4 or an ammonium group substituted by 1 to 4 hydrocarbon groups. The compounds of formula I may be prepared from the corresponding diamine.
Description
BIODEGRADABLE SEOUESTRANTS FOR DETERGENT COMPOSITIONS
The present invention relates to the use of biodegradable sequestrants in detergent compositions, as well as to a process for preparing such seguestrants.
Numerous~domestic or industrial detergent compositions contain oxygen-containing bleaching agents such as in particular sodium perborate or sodium percarbonate.
It is known that the efficiency of these bleaching agents in detergent compositions is reduced when the water used for the washing or the materials that are to be washed contain metal ions such as for example manganese, copper and iron ions. These ions react with the bleaching agents containing peroxides or generating peroxides, thus causing the partial decomposition of the said bleaching agents and, consequently, the reduction in their concentration during the washing operation.
Other components of the detergent compositions may also be decomposed or deactivated by metal ions.
The incorporation of sequestrants makes it possible to avoid or to limit the decomposition of the bleaching agents and the decomposition or the deactivation of other components such as enzymes or brighteners.
A tendency also exists to incorporate in the detergent compositions compounds of natural origin such as surface-active agents derived from vegetable oil.
These compounds can undergo decomposition catalysed by traces of metals. The presence of sequestrants of metal ions therefore also enables their preservation.
Finally, the detergent compositions contain builders which have the essential role of complexing the calcium and magnesium ions present in hard waters and therefore of maintaining them in solution. The presence of builders generally prevent the deposition or the precipitation of insoluble calcium and/or magnesium compounds, and more particularly their deposition on the clean surface of the item to be cleaned.
In this manner, a greater proportion of the surface-active agents of the detergent compositions remains available and the efficiency of the compositions is thereby improved.
Among the actual sequestrants and the builders normally used, ethylenediaminetetraacetate acid and its sodium derivatives (EDTA), nitrilotriacetic acid (NTA), phosphates and phosphonates may be mentioned.
EDTA and other similar compounds exhibit a good complexing power for heavy metals, but suffer from the major disadvantage of their very low biodegradability; which may lead to their banning, at least partially, in future.
NTA is suspected of being carcinogenic and/or teratogenic and its use is banned for detergent compositions in some states in the United States and in some European countries.
Phosphates, such as in particular sodium tripolyphosphate, end up, in the absence of a plant for sewage purification, in water courses and in lakes where they accelerate the growth of algae; they are therefore currently accused of participating in the phenomenon of eutrophication of lakes and water courses.
The use of aminoethylene phosphonates appears to pose a similar problem.
In order to remedy these disadvantages, other complexing agents exhibiting better biodegradability have been proposed.
Thus, Patent EP-A-0 287, 885 describes the use of N,N-bis(carboxymethyl)-2-amino-2- hydroxymethylacetic acid and its alkali metal, ammonium and substituted ammonium salts, as complexing agents in detergent compositions containing a bleaching agent.
Patent US 4,827.014 relates to the use of compounds which are isomers of the preceding compounds, N,N-bis (carboxymethyl) -3-antino-2- hydroxypropionic acid and its alkali metal, ammonium and substituted ammonium salts in the same type of detergent compositions.
It happens, however, that the complexing power of these compounds is not as good as that of EDTA for all the metal ions present; in addition, the parent compounds from which these compounds are synthesised are relatively expensive.
New research initiated by the applicant has led to the present invention.
The latter thus relates to detergent compositions for domestic use or for industrial use, characterised in that they comprise at least one sequestrant chosen. from the compounds of general formula (I)
in which:
- n represents a number from 1 to 6,
- the symbols M1, M2, M3, M4 and not, identical
or different, represent: . a hydrogen atom, . an alkali metal, . an ammonium group -NiX or an ammonium
group substituted by 1 to 4 organic
groups.
Preferably, in the formula (I) of the sequestrants used:
- n represents a number from 1 to 6,
- the symbols M1, M2, M3, M4 and M5, identical
or different, represent: * a hydrogen atom, . a sodium or potassium atom, . an NEX group, a a monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium
group, the alkyl radical or radicals,
linear or branched, having 1 to 4 carbon
atoms.
In the detergent compositions of the invention, a sequestrant or sequestrants of general formula (I) will be preferably used, in which:
- n represents a number from 2 to 4,
- the symbols M1, M2, M3, M4 and M5, identical
or different, represent a hydrogen atom or
a sodium atom.
As nonrestrictive examples of sequestrants of formula (I), there may be mentioned the pentasodium or tetrasodium salts of N,N,N',N'- tetra(carboxymethyl)-2,6-diaminohexanoic acid, the pentasodium or tetrasodium salts of N,N,N',N' tetra (carboxymethyl) -2, 5-diaminopentanoic acid, the pentasodium or tetrasodium salts of N,N,N',N'tetra(carboxymethyl)-2,4-diaminobutyric acid.
The sequestrants of formula (I) may be either levorotatory (L), dextrorotatory (D) or DL.
Mixtures of several sequestering agents of formula (I) may also be used without departing from the framework of the invention.
The amount of sequestrant of formula (I) in the detergent compositions may vary widely, in particular depending on the type of detergent composition.
Generally, the sequestrant of formula (I) represents 0.01 % to 20 % and preferably 0.05 % to 10 % by weight relative to the total dry weight of the detergent composition.
Total dry weight of the detergent composition, in the present account, is understood as meaning the total weight of the various constituents of the said detergent composition with the exception of the water optionally present in particular in liquid detergent compositions.
As previously indicated, the amount of sequestrant of formula (I) in the detergent compositions varies depending on whether their role is that of avoiding or slowing down the decomposition of the bleaching agents of the perborate type, or of replacing all or part of the builders present in the said detergent compositions.
When the sequestrant of formula (I) is present essentially in order to avoid the decomposition of the bleaching agents, amounts of 0.05 % to 2 % by weight per total dry weight of the detergent composition are sufficient.
In contrast, if it is desired to replace at least part of the builders in the detergent composition by the sequestrant of formula (I), the amount of the latter will be most often 1 * to 20 %.
In the industrial detergent compositions used in particular for washing hard surfaces like metal surfaces, glass, car bodies, the role of the sequestrant of formula (1) is more particularly to form a complex with calcium ions and it may, in that case, represent 0.01 % to 5 % by weight per weight.
The detergent compositions also normally contain various constituents which may differ depending on the type of detergent composition.
Thus, as a guide, they normally contain about 5 to 25 % by weight per weight of surface-active agents, 15 to 50 % by weight per weight of builders (part of which at least may consist of the sequestrants of formula (I)), with or without co-builders, 5 to 35 % by weight per weight of bleaching agents with or without activators of the said bleaching agents, and other constituents such as enzymes, antifoaming agents, corrosion inhibitors, brighteners, perfumes, colorants, formulation adjuvants, fillers and, optionally, water.
The surface-active agents which are generally suitable in the detergent compositions contain one or more anionic, zwitterionic or nonionic hydrophilic organic radicals.
Among the anionic surface-active agents, sulphonates, sulphates and carboxylates may be mentioned in particular. The sulphonates are more particularly alkylbenzenesulphonates, alkylsulphonates, hydroxyalkylsulphonates and esters of sulphonated fatty acids. The sulphates are more particularly sulphuric monoesters of primary alcohols or secondary alcohols, sulphates of fatty alkanolamines, of fatty acids monoglycerides or of the reaction products of ethylene oxide with primary or secondary fatty alcohols or alkylphenols. The carboxylates are more particularly fatty esters or amides of hydroxycarboxylic or aminocarboxylic acids. These anionic surface-active agents may be present in the form of their sodium, potassium or ammonium salts or of organic bases like monoethanolamine, diethanolamine and triethanolamine.
The nonionic surface-active agents may be for example condensation compounds of 3 to 40 moles of ethylene oxide per mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulphonamide.
The builders normally used in the detergent compositions are more particularly sodium carbonate, sodium silicate, phosphates like sodium pyrophosphate, sodium tripolyphosphate, the other sodium polyphosphates or sodium metaphosphate, alkanepolyphosphonates, aminoalkanepolyphosphonates, hydroxyalkanepolyphosphonates, phosphonocarboxylates or zeolites. The builders are frequently combined with cobuilders like carboxylic polyacids such as polymers of acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid or citraconic acid; carboxymethyl ethers of sugars, starch and cellulose may also be mentioned as co-builders.
The bleaching agents are in particular peroxide derivatives like for example hydrated sodium perborates, peroxycarbonates, peroxyphosphonates.
Activators of these bleaching agents are often used; they are for example N-acylated or O-acylated compounds.
The sequestrants of formula (I) may be obtained in particular from diaminocarboxylic acids of general formula (II):
in which n represents a number from 1 to 6 and preferably from 2 to 4, by reaction with sodium chloroacetate.
Generally, the reaction is carried out in solution in water and at a temperature of 25C to lOOC and preferably 40'C to 90C without these values having a critical importance.
Among the diaminocarboxylic acids of formula (II), lysine (n = 4) is very particularly advantageous because of its relatively low cost.
Ornithine (n = 3) and 2,4-diaminobutyric acid (n = 2) may also be mentioned.
Lysine and ornithine are the two preferred diaminocarboxylic acids of formula (ZI) enabling the preparation of the most advantageous sequestrants of formula (I) both for their sequestering qualities and for their biodegradable character.
Another process for preparing the sequestrants of formula (I) consists in reacting diaminocarboxylic acid with an alkali metal cyanide and formaldehyde.
This reaction is normally carried out in water, in a water-miscible solvent or in a mixture of water and such a solvent, at a temperature of 250C to 100"C and preferably 40"C to 90"C. If water is present during the reaction then the sequestrant of formula I may be formed directly by this reaction. If water is not present and the solvent is e.g. a water-miscible solvent, then a nitrile compound is produced, which is then hydrolysed to give the desired compound. The hydrolysis may be carried out in situ or after isolation of the nitrile compound.
The following examples illustrate the invention.
Example 1
Preparation of the pentasodium salt of N.N.N'.N' tetra(carboxvmethvl)-2,6-diaminohexanoic acid
146 g (1 mol) of lysine were dissolved in
400 g of water and the solution obtained was heated to
650C.
480 g (4.12 mol) of sodium chloroacetate were
added in portions in 1 hour with stirring.
600 g of an aqueous solution containing 27 %
by weight of sodium hydroxide (4.05 mol of NaOH) were
then progressively added at a rate enabling the pH to
be maintained between 8.8 and 9.2. During the addition
of sodium hydroxide, the temperature was allowed to
rise up to a maximum of 850C.
At the end of the addition, the reaction
mixture was again stirred for 2 hours at 880C and then
the temperature was raised to the reflux temperature
for 30 minutes.
The reaction mixture was allowed to cool to
room temperature; sodium chloride precipitated during
this cooling. Next, the mixture was filtered at room
temperature.
The filtrate was allowed to stand overnight
and another amount of sodium chloride then
precipitated.
After another filtration, the filtrate was diluted with 1500 g of water, it was then acidified to about pH 1 with 800 g of hydrochloric acid at 36 % by weight.
After inoculation by seeding, the crystallisation occurred slowly. After allowing to stand overnight, the product was filtered, washed abundantly with water and finally suspended in 1000 g of water and heated with stirring at 800C.
After cooling, the solid was filtered and dried at 800C under vacuum.
250 g of N,N,N',N'tetra(carboxymethyl)-2,6-diaminohexanoic acid with a melting point of 216-220"C were thus obtained (yield of 66 % relative to the lysine used).
The corresponding pentasodium salt is easily prepared by neutralising the different carboxylic functional groups by means of a solution of sodium hydroxide.
Example 2
305.5g of lysine was dissolved in 600 mls of water and, 161.2g of 100 TW (47%) sodium hydroxide solution, and 10.8g of sodium cyanide solution (30%) were then added.
The contents of the flask were heated to 67"C 70OC, and sodium cyanide solution (1572g) and formaldehyde solution (929.2g) were then added continuously over a period of 5.5 hours via peristaltic pumps.
During the early stages of the addition an exotherm produced by the reaction of the cyanide and formaldehyde was sufficient to bring the temperature of the reaction mixture to 97"C - 98"C. The bulk of the addition was carried out at the boiling point at atmospheric pressure.
After all the cyanide had been added, the formaldehyde addition was stopped and the cyanide level of the reaction mixture was checked and found to be 3050 ppm.
This level was reduced to below 3 ppm by addition of formaldehyde (to a total of 929.2g)
Throughout the addition, ammonia solution was distilled from the reaction and a total of 1610 ml was collected.
The weight of solution remaining at the end of all additions was 1700g with an initial N,N,N',N'tetra(carboxymethyl)-2,6-diaminohexanoic acid [Lysta] content of 44%. This was diluted to give a solution of nominally 30% Lysta (Acid).
Final Weight 2636 g
Final Assay 29.6 % Lysta (Acid)
ExamPle 3 Comnlexina power of the seauestrants of formula (I) The capacity of a sequestrant to fix metal ions such as Fe, Cu or Ca and to inhibit their effect may be measured for example by the following method.
A suitable amount of the sequestrant to be tested (T.S.) is dissolved in 100 cm3 of water. The pH is adjusted to 10 by means of a N solution of sodium hydroxide and maintained at this value during the titration by successive additions of N solution of sodium hydroxide.
This solution is titrated at room temperature with a 0.05 M solution of a salt of the metal to be complexed (for example ferric chloride, cupric chloride, calcium carbonate).
The end point of the titration is visualised by the onset of a sudden increase in the cloudiness of the solution measured, for example, by means of a light photometer.
The complexing power is expressed as a molar ratio sequestrant/metal ion: the lower this ratio, the better the complexing power of the test compound.
Tests were carried out on various compounds: (A) pentasodium salt of N,N,N',N'
tetra(carboxymethyl)-2,6-diaminohexanoic
acid (prepared in Example 1) (LYSTA); (B) pentasodium salt of N,N,N',N'
tetra (carboxymethyl)-2,5-diaminopentanoic
acid (ORNTA); (C) tetrasodium salt of ethylenediaminetetraacetic
acid (EDTA) by way of comparison; (D) trisodium salt of 2-hydroxy-N,N
bis (carboxymethyl)-3-aminopropionic acid
(or trisodium salt of isoserine-N,N-diacetic
acid:ISDA) by way of comparison (US 4, 827, 014).
The results obtained are collated in Table 1 below.
Molar ratio sequestrant/ion Examples Sequestrants Ca++ Cu++ Fe3+ 3A LYSTA 1/2 1/2 1/2 3B ORNTA 1/1.5 1/1.5 1/1.3 3C I EDTA I 1/1 1/1 1/0.4 3D ISDA 1/0.6 1/1.6 1/4 TABLE 1
It is observed that the 2 compounds of the invention have a substantially higher complexing power than EDTA which is commonly used in detergent compositions and that they also have a higher complexing power for calcium than ISDA, and of the same order of magnitude for copper as ISDA.
Example 4
Stabilisation of sodium perborate
A standard detergent composition of the following composition by weight is prepared:
- sodium dodecylbenzenesulphonate: 7.0 %
- ethoxylated ketostearyl alcohol
(11 moles of ethylene oxide): 8.0 %
- sodium tripolyphosphate: 25.0 %
- sodium metasilicate, 5 H2O: 6.0 %
- sodium perborate, 4 H2O: 15.4 %
- sodium carbonate: 6.0 % - anhydrous sodium sulphate: 32.6 %
Using this detergent composition, solutions at a concentration of 6.5 grams/litre are prepared in distilled water.Defined amounts (expressed in 10-6 g/g of solution or ppm) of Fe3+, Cu2+ and Mn2+ ions are added to these solutions as well as 0.9 % (by weight relative to the weight of the detergent composition in solution) of a sequestrant: (A) pentasodium salt of N,N,N',N'
tetra(carboxymethyl)-2,6-diaminohexanoic
acid (prepared in Example 1) (LYSTA): invention (B) pentasodium salt of N,N,N',N' tetra (carboxymethyl) -2, 5-diaminopentanoic acid (ORNTA): invention (C) tetrasodium salt of ethylenediaminetetraacetic
acid (EDTA): prior art (D) trisodium salt of 2-hydroxy-N,N
bis(carboxymethyl)-3-aminopropionic acid
(ISDA): prior art.
These various solutions, as well as control solutions without sequestrant, are maintained 2 hours at 800C.
After this treatment, the amount of undecomposed sodium perborate is assayed in each of these solutions.
The results obtained are collated in Table below.
Fe3+ Cu2 xn2+ Seques- % of per Examples (in ppm) (in ppm) (in ppm) trant borate remainin Control 0.6 | 0.25 0.25 None | 0 4A 0.6 0.25 0.25 0.9 % 42 LYSTA 4B 0.6 0.25 0.25 0.9 % 51 ORNTA 4C 0.6 0.25 0.25 0.9 % 38 EDTA 4D 0.6 0.25 0.25 0.9 % 21 ISDA
TABLE 2
It is observed that the sequestrants of formula (I) of the invention are more effective than
EDTA and, in particular ISDA of the prior art for stabilising sodium perborate.
Claims (11)
1. Detergent composition for domestic use or for industrial use, characterised in that it comprises at least one sequestrant chosen from the compounds of general formula (I)
in which:
- n represents a number from 1 to 6,
- the symbols M;, M2, M3, M4 and M5, identical
or different, represent: . a hydrogen atom,
an alkali metal,
an ammonium group -NE or an ammonium
group substituted by 1 to 4 organic
groups
2.Composition according to claim 1, characterised in that in the formula (I) of the sequestrants used:
- n represents a number from 1 to 6,
- the symbols M1, M2, M3, M4 and M5, identical
or different, represent:
a hydrogen atom, . a sodium or potassium atom, . an NH group, . a monoalkylammonium, dialkylammonium,
trialkylammonium or tetraalkylammonium
group, the alkyl radical or radicals,
linear or branched, having 1 to 4 carbon
atoms.
3. Composition according to claim 1, characterised in that in the formula (I) of the sequestrants used:
- n represents a number from 2 to 4,
- the symbols M1, M2, M3, M4 and Ms, identical
or different, represent a hydrogen atom or
a sodium atom.
4. Composition according to one of claims 1 to 3, characterised in that the sequestrant of formula (I) is chosen from the pentasodium or tetrasodium salts of N,N,N',N'tetra(carboxymethyl)-2,6-diaminohexanoic acid, the pentasodium or tetrasodium salts of N,N,N',N' tetra (carboxymethyl) -2, 5-diaminopentanoic acid the pentasodium or tetrasodium salts of N,N,N',N'tetra(carboxymethyl)-2,4-diaminobutyric acid.
5. Composition according to one of claims 1 to 4, characterised in that the sequestrant of formula (I) represents 0.01 % to 20 % and preferably 0.05 % to 10 % by weight relative to the total dry weight of the detergent composition.
6. Composition according to one of claims 1 to 5, characterised in that it contains 5 to 25 % by weight per weight of surface-active agents, 15 to 50 % by weight per weight of builders, with or without co-builders, 5 to 35 % by weight per weight of bleaching agents with or without activators of the said bleaching agents, and other constituents such as enzymes, antifoaming agents, corrosion inhibitors, brighteners, perfumes, colorants, formulation adjuvants, fillers and, optionally, water.
7. Process for preparing the sequestrants of formula (I) used in the composition according to one of claims 1 to 6, characterised in that they are obtained by reacting diaminocarboxylic acids of general formula (If):
in which n represents a number from 1 to 6 and preferably from 2 to 4, with sodium chloroacetate.
8. Process according to claim 7, characterised in that the reaction is carried out in solution in water and at a temperature of 250C to 100eC and preferably 40 C to 900C.
9. Process according to one of claims 7 or 8, characterised in that the diaminocarboxylic acid of formula (11) is chosen from lysine (n = 4), ornithine (n = 3), and 2,4-diaminobutyric acid (n = 2) and is preferably lysine.
10. Process for preparing the sequestrants of formula (I) used in the composition according to one of claims 1 to 6, characterised in that they are obtained by reacting diaminocarboxylic acids of general formula (II):
in which n represents a number from 1 to 6 and preferably from 2 to 4, with an alkali metal cyanide and formaldehyde, in the presence of water, at a temperature of 25"C to 100"C and preferably 400C to 90"C.
11. Process for preparing a sequestrant of formula (I) used in the composition according to one of claims 1 to 6, characterised in that it is obtained by reacting a diaminocarboxylic acid of general formula II
in which n represents a number from 1 to 6 and preferably from 2 to 4, with an alkali metal cyanide and formaldehyde, in the absence of water, at a temperature of 25C to 100"C, and preferably 40C to 90"C, and hydrolysing the resulting product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9123402A GB2261218A (en) | 1991-11-05 | 1991-11-05 | Biodegradable sequestrants for detergent compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9123402A GB2261218A (en) | 1991-11-05 | 1991-11-05 | Biodegradable sequestrants for detergent compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9123402D0 GB9123402D0 (en) | 1991-12-18 |
| GB2261218A true GB2261218A (en) | 1993-05-12 |
Family
ID=10704045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9123402A Withdrawn GB2261218A (en) | 1991-11-05 | 1991-11-05 | Biodegradable sequestrants for detergent compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2261218A (en) |
-
1991
- 1991-11-05 GB GB9123402A patent/GB2261218A/en not_active Withdrawn
Non-Patent Citations (12)
| Title |
|---|
| Chemical Absracts 100 (13): 103831j * |
| Chemical Abstracts 102 (5): 46238m * |
| Chemical Abstracts 102(6):51722u * |
| Chemical Abstracts 105 (23): 208376w * |
| Chemical Abstracts 106(4):23955m * |
| Chemical Abstracts 109(18):157410a * |
| Chemical Abstracts 109(26):238263g * |
| Chemical Abstracts 112(12): 106135u * |
| Chemical Abstracts 86 (18): 128301s * |
| Chemical Abstracts 87(4):29839n * |
| Chemical Abstracts 93 (8): 81513q * |
| Chemical Abstracts 97(2):8578t * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9123402D0 (en) | 1991-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3692685A (en) | Detergent compositions | |
| US6264839B1 (en) | Phosphonomethylated polyvinylamines and preparation and use thereof | |
| US5362412A (en) | Biodegradable bleach stabilizers for detergents | |
| JP2557832B2 (en) | Novel ether polycarboxylate | |
| US4663071A (en) | Ether carboxylate detergent builders and process for their preparation | |
| US4046707A (en) | Treatment of aqueous systems | |
| US3914297A (en) | Carboxy methyloxy succinates | |
| AU608592B2 (en) | Preparation of serine-N, N-diacetic acid and derivatives as complexing agents and detergents containing same | |
| FI111260B (en) | Process for phosphonating a compound, phosphonated oligomer or carbon oligomer of an active olefin and its use in water treatment | |
| US3776850A (en) | Detergent formulations | |
| GB2138853A (en) | Bleach compositions | |
| AU601921B2 (en) | 2-hydroxy-3-aminopropionic-n,n-diacetic acid and derivatives thereof, preparation thereof, and detergents containing same | |
| RU2003132068A (en) | CORROSION INHIBITORS FOR WATER SYSTEMS | |
| EP0695289B1 (en) | Hydroxamic acids and hydroxamic acid ethers and their use as complexing agents | |
| CA2013847C (en) | 2-methyl- and 2-hydroxymethyl-serine-n,n-diacetic acid and derivatives thereof | |
| AU2009207668B2 (en) | Surface treatment composition containing phosphonic acid compounds | |
| US5112530A (en) | Use of 2-hydroxy-3-aminopropionic acid derivatives as complexing agents, bleach stabilizers and builders in detergent compositions | |
| GB2261218A (en) | Biodegradable sequestrants for detergent compositions | |
| US3784486A (en) | Alpha,alpha-carboxyalkoxy succinic acid compounds as detergent builders and sequestering agents | |
| US20220010239A1 (en) | Detergent polymer and composition | |
| US4107064A (en) | Metal sequestering method | |
| US4066687A (en) | 2,3-carboxy alkoxy succinic acid and salts thereof | |
| CA2240321A1 (en) | An amino nitrile intermediate for the preparation of 2-hydroxyethyl iminodiacetic acid | |
| GB2236752A (en) | Aminophosphinates and cleaning compositions containing them | |
| JP2002515922A (en) | Polyaminomonosuccinic acid derivative-degradable chelating agent, its use and composition thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |