Aqueous formulations with good storage capabilities

Abstract

Aqueous formulations comprising (A) at least one organic complexing agent selected from (A1) alkali metal salts of aminopolycarboxylic acids and (A2) polymers bearing at least two CH.sub.2N(CH.sub.2COOH)-units per molecule, partially or fully neutralized with alkali, (B) at least one salt of at least one of the following acids: nitric acid, sulphuric acid, sulphamic acid, methanesulfonic acid, C.sub.1-C.sub.2-carboxylic acids, C.sub.2-C.sub.4-hydroxymonocarboxylic acids, C.sub.2-C.sub.7-dicarboxylic acids, unsubstituted or substituted with hydroxyl, and C.sub.4-C.sub.6-tricarboxylic acids, each unsubstituted or substituted with hydroxyl, (C) at least one compound selected from (C1) phosphoric acid C.sub.2-C.sub.10-monoalkyl esters, (C2) a C.sub.3-C.sub.10-alkynol, optionally alkoxylated with one to 10 alkoxide groups per hydroxyl group, and (C3) a C.sub.4-C.sub.10-alkynediol, optionally alkoxylated with one to 10 alkoxide groups per hydroxyl group, said aqueous formulations having pH values in the range of from 7.5 to 10.

Claims

1. An aqueous formulation, comprising: (A) an organic complexing agent comprising (A1) an alkali metal salt of an aminopolycarboxylic acid, (A2) a polymer bearing at least two C.sub.2N(CH.sub.2COOH)-units per molecule, at least partially neutralized with alkali, or a mixture of two or more of any of these; (B) an acid salt comprising, in salt form, nitric acid, sulfuric acid, sulfamic acid, methanesulfonic acid, a C.sub.1-C.sub.2-carboxylic acid, a C.sub.2-C.sub.4-hydroxymonocarboxylic acid, a C.sub.2-C.sub.7-dicarboxylic acid, a C.sub.4-C.sub.6-tricarboxylic acid, the di and tri carboxylic acids being optionally substituted with hydroxyl, or a mixture of two or more of any of these; and (C) a compound of formula (i), a compound of formula (ii), a compound of formula (iii), and/or a compound of formula (iv)
(MO).sub.2P(O)OR.sup.2(i),
HCCCH.sub.2O(CH.sub.2CHR.sup.3O).sub.nH(ii),
H(OCHR.sup.3CH.sub.2).sub.nOCH.sub.2CCCH.sub.2O(CH.sub.2CHR.sup.3O).sub.mH(iii), and/or
H(OCHR.sup.3CH.sub.2).sub.nOCH.sub.2CH.sub.2CCCH.sub.2CH.sub.2O(CH.sub.2CHR.sup.3O).sub.mHiv), R.sup.2 being methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, n-pentyl, iso-pentyl, sec-pentyl, iso-amyl, or C.sub.6-C.sub.10-alkyl, R.sup.3 being independently H, methyl, or ethyl, m and n being independently in a range of from 1 to 4.2, and M being independently Na or K, wherein (C) is present in an amount from greater than 0 wt. % to 1.5 wt. %, further wherein the aqueous formulation has a pH value in a range of from 7.5 to 10.

2. The formulation of claim 1, having a pH value in a range of from 8.5 to 10.

3. The formulation of claim 1, having a total solids content in a range of from 20 to 45%.

4. The formulation of claim 1, wherein the organic complexing agent (A1) is present and comprises an alkali metal salt of methylglycine diacetic acid, glutamic acid diacetic acid, nitrilotriacetic acid, ethylendiamine tetraacetate, or diethylenamine triamine pentaacetate.

5. The formulation of claim 1, wherein the organic complexing agent (A2) is present and comprises an at least partially carboxymethylated polyethylenimine.

6. The formulation of claim 1, wherein the compound (C) comprises the compound of formula (ii), alkoxylated with 1 to 3 moles of ethylene oxide and/or propylene oxide per mole.

7. The formulation of claim 1, wherein the compound (C) comprises the compound of formula (iii), alkoxylated with 1 to 10 molecules of ethylene oxide and/or propylene oxide per hydroxyl group.

8. The formulation of claim 1, comprising: from 10 to 45 wt. % of the complexing agent (A); from 1 to 15 wt. % of the salt (B); and from 0.01 to 1.5 wt. % of the compound (C), percentages referring to an entire aqueous formulation.

9. The formulation of claim 1, wherein the complexing agent (A) comprises a sodium and/or potassium salt of the aminopolycarboxylic acid (A1).

10. The formulation of claim 1, wherein the complexing agent (A) is of formula (I):
[R.sup.1CH(COO)N(CH.sub.2COO).sub.2]M.sub.3-xH.sub.x(I), wherein M is independently an alkali metal cation, x is in a range of from zero to 0.8, and R.sup.1 is CH.sub.2OH or C.sub.1-C.sub.4-alkyl.

11. The formulation of claim 1, wherein the complexing agent (A) is of formula (II):
[OOCCH.sub.2CH.sub.2CCH(COO)N(CH.sub.2COO).sub.2]M.sub.4-xH.sub.x(II), wherein M is independently an alkali metal cation, and x is in a range of from zero to 0.8.

12. The formulation of claim 1, further comprising: an anionic surfactant, a non-ionic surfactant, or a mixture of two or more of any of these.

13. A cleaning formulation, comprising: the formulation of claim 1.

14. A process for manufacturing a cleaning formulation, the process comprising: mixing the formulation of claim 1 with water.

15. A process for manufacturing the formulation of claim 1, the process comprising: mixing (A) the complexing agent (A), the acid salt (B), and the compound (C), in one or more steps with water.

16. An aluminum container, comprising the formulation of claim 1.

17. The formulation of claim 1, wherein the compound (C) comprises the compound of formula (i)
(MO).sub.2P(O)OR.sup.2(i), wherein R.sup.2 is C.sub.6-C.sub.10-alkyl, and M is independently Na or K.

18. The formulation of claim 1, wherein the compound (C) comprises the compound of formula (i)
(MO).sub.2P(O)OR.sup.2(i), wherein R.sup.2 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, n-pentyl, iso-pentyl, sec-pentyl, iso-amyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, or iso-decyl, and M is independently Na or K.

19. The formulation of claim 1, wherein the compound (C) comprises the compound of formula (ii)
HCCCH.sub.2O(CH.sub.2CHR.sup.3O).sub.nH(ii), wherein R.sup.3 is independently H, methyl, or ethyl, and n is in a range of from 1 to 4.2.

20. The formulation of claim 1, wherein the compound (C) comprises the compound of formula (iii) and/or (iv)
H(OCHR.sup.3CH.sub.2).sub.nOCH.sub.2CCCH.sub.2O(CH.sub.2CHR.sup.3O).sub.mH(iii) and/or
H(OCHR.sup.3CH.sub.2).sub.nOCH.sub.2CH.sub.2CCCH.sub.2CH.sub.2O(CH.sub.2CHR.sup.3O).sub.mH(iv), wherein R.sup.3 is independently H, methyl, or ethyl, and m and n are independently in a range of from 1 to 4.2.

Description

(1) The invention is further illustrated by working examples.

(2) General Remark:

(3) Aqueous solutions were prepared by mixing the following components:

(4) In accordance with Table 1, a beaker was charged with 40% by weight aqueous solution of complexing agent (A). Then, the corresponding acid of salt (B) was added until the respective pH value was reached. Subsequently, ten percent water and the amount of compound (C) according to Table 1 were added. The respective inventive solutionsor the respective comparative solutions, as the case may bewere obtained.

(5) The corrosion tests were performed as follows:

(6) An amount of 100 ml of inventive solution or comparative solution, as the case may be in each case hereinafter referred to as test solutionwas put into a sealable plastic beaker. An aluminium plate with the following properties: 99.5% Al, size 20 mm50 mm1 mm, density 2.7 g/cm.sup.3, obtained from Rocholl GmbH, 74858 Aglasterhausen, Germany, was cleaned with acetic acid ethylester, dried and weighed and then immediately placed into the test solution in such a way that it is completely immersed and the main surfaces had no contact with the bottom or the wall of the beaker. The beaker was then placed in a heating chamber at 55 C.

(7) After 7 days the aluminium plate was removed from the test solution, cleaned thoroughly with distilled water and a sponge, dried and weighed.

(8) The weight loss per year [mm per year] is calculated as follows:

(9) Weight loss (mm/year) is the weight loss in G as determined, multiplied by 365 days/year and by 10, and normalized by division by 2.7 g/cm.sup.3, by the surface of 2.14 cm.sup.2, and by 7 days.

(10) I. Manufacture of Inventive Formulations and of Comparative Formulations

(11) The following substances were used:

(12) (A1.1): (D,L)-MGDA-Na.sub.3 as 40% by weight aqueous solution

(13) (A1.2): (D,L)-GLDA-Na.sub.4 as 40% by weight aqueous solution

(14) (A1.3): NTA-Na.sub.3 as 40% by weight aqueous solution

(15) (A1.4): EDTA-Na.sub.4 as 40% by weight aqueous solution

(16) (A1.5): DTPA-Na.sub.5 as 40% by weight aqueous solution

(17) (B.1): citric acid in bulk,

(18) (B.2): methyl sulfonic acid, as 70% by weight aqueous solution

(19) (B.3): sulfuric acid as 96% aqueous solution

(20) (B.4): nitric acid as 65% by weight aqueous solution

(21) (B.5): acetic acid

(22) (B.6): formic acid

(23) (C1.1): (MO).sub.2P(O)OC.sub.6-C.sub.10-alkyl and MO-P(O)(OC.sub.6-C.sub.10-alkyl).sub.2, C.sub.6-C.sub.10-alkyl being a combination from the respective normal alkyl groups

(24) (C2.1): HCCCH.sub.2O(PO).sub.1.3H (PO: propylene oxide). N=1.3 refers to the average value.

(25) As comparative corrosion inhibitors, the following substances were used:

(26) ##STR00006##

(27) The following inventive formulations (AF) and comparative formulations C-(AF) were made, see Table 1.

(28) II. Results of Corrosion Tests

(29) The average aluminium abrasion was determined as explained above. The results are summarized in Table 1. They are average values of 2 tests.

(30) TABLE-US-00001 TABLE 1 Composition and corrosion test results of inventive formulations and comparative formulations % by weight % by weight (ac- pH Al abrasion Name Ingredient [g] tel quel tive ingredient) value [mg/a] C-(AF.1) (A1.1) 164.3 82.2 32.9 9.0 1.74 (B.1) 15.7 7.9 7.9 water 20.0 10.0 (AF.2) (A1.1) 181.2 87.0 34.8 9.0 0.49 (B.1) 17.3 8.3 8.3 (C2.1) 1.5 0.7 0.5 Water 8.3 4.0 C-(AF.3) (A1.1) 180.6 72.7 29.1 9.0 4.9 (B.1) 17.3 6.9 6.9 C-(C.10) 2.1 0.9 0.9 Water 48.6 19.5 C-(AF.4) (A1.1) 180.2 72.5 29.0 9.0 2.59 (B.1) 17.2 6.9 6.9 C-(C.11) 2.5 1.0 0.5 Water 33.9 13.6 C-(AF.5) (A1.1) 154.3 85.7 34.3 9.0 7.57 (B.2) 25.7 14.3 10.0 C-(AF.6) (A1.1) 154.3 77.1 34.3 9.0 9.12 (B.2) 25.7 12.9 10.0 water 20.0 10.0 (AF.7) (A1.1) 170.2 83.5 33.4 9.0 0.76 (B.2) 28.3 13.9 9.7 (C2.1) 1.5 0.7 0.5 Water 3.7 1.8 C-(AF.8) (A1.1) 169.6 72.3 28.9 9.0 4.89 (B.2) 28.3 11.4 8.0 C-(C.10) 2.1 0.9 0.4 Water 34.7 13.9 C-(AF.9) (A1.1) 169.3 72.3 28.9 9.0 9.83 (B.2) 28.2 11.4 8.0 C-(C.11) 2.5 0.9 0.4 Water 33.9 13.9 C-(AF.10) (A1.1) 168.6 82.1 32.8 9.0 7.42 (B.1) 28.1 13.7 9.6 C-(C.12) 2.5 1.2 0.4 water 6.2 3.0 (AF.11) (A1.1) 171.3 85.3 34.1 9.0 0.01 (B.1) 28.6 14.2 10.0 (C1.1) 1.0 0.5 0.5 (AF.12) (A1.1) 171.3 73.3 29.3 9.0 0.62 (B.1) 28.6 12.2 8.5 (C1.1) 0.1 0.04 0.04 Water 33.9 14.5 C-(AF.13) (A1.1) 500 80 32.0 9.0 8.72 (B.4) 62.5 10 6.5 Water 62.5 10 (AF.14) (A1.1) 176.5 79.4 31.8 9.0 0.62 (B.4) 22.0 9.9 6.4 (C2.1) 1.5 0.7 0.4 Water 22.2 10.0 C-(AF.15) (A1.1) 500.0 84.2 33.7 9.0 8.40 (B.5) 34.6 5.8 5.8 Water 59.4 10.0 (AF.16) (A1.1) 185.7 83.6 33.4 9.0 0.95 (B.5) 12.8 5.8 5.8 (C2.1) 1.5 0.7 0.4 Water 22.2 10.0 C-(AF.17) (A1.1) 500.0 85.1 34.0 9.0 8.89 (B.6) 28.9 4.9 4.9 Water 58.8 10.0 (AF.18) (A1.1) 187.7 84.5 33.8 9.0 0.88 (B.6) 10.8 4.9 4.9 (C2.1) 1.5 0.7 0.4 Water 22.2 10.0 C-(AF.19) (A1.1) 500.0 85.0 34.0 9.0 10.59 (B.3) 29.2 5.0 4.8 Water 58.8 10.0 (AF.20) (A1.1) 187.6 84.4 33.8 9.0 1.27 (B.3) 11.0 4.9 4.9 (C2.1) 1.5 0.7 0.4 Water 22.2 10.0 C-(AF.21) (A1.2) 495.0 83.8 33.5 9.0 9.80 (B.2) 36.7 6.2 4.3 Water 59.1 10.0 (AF.22) (A1.2) 184.8 83.2 33.3 9.0 1.39 (B.2) 13.7 6.2 4.3 (C2.1) 1.5 0.7 0.4 Water 22.2 10.0 C-(AF.23) (A1.1) 500.0 78.0 31.2 9.0 5.93 (B.2) 77.2 12.0 8.4 Water 64.1 10.0 (AF.24) (A1.1) 184.8 77.4 31.0 9.0 0.08 (B.2) 13.7 11.9 8.4 (C2.1) 1.5 0.7 0.4 Water 22.2 10.0 C-(AF.25) (A1.1) 191.9 86.4 34.5 11.0 20.5 (B.2) 6.6 3.0 2.1 (C1.1) 1.5 0.7 0.4 Water 22.2 10.0