JPS586981A - Aluminum surface detergent non-fluoride acidic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aluminum surface cleaning composition containing sulfuric acid, phosphoric acid and at least one surfactant, and a method thereof.

Aluminum and aluminum alloy containers are manufactured by drawing and forming operations commonly referred to as drawing and ironing. This operation results in the deposition of lubricant and molding oil on the container surface. As a result, residual aluminum flakes are deposited on the surface and are present in relatively large amounts on the inner surface of the container.

Before a container is subjected to, for example, chemical treatment or sanitary lacquering, the surface of the container must be cleaned and drained so that no contaminants remain on the surface which would interfere with further processing of the container.

A composition currently used commercially to clean such aluminum containers is an aqueous sulfuric acid solution containing hydrofluoric acid and one or more surfactants. Although such cleaning solutions are very effective and have many advantages, there are also certain disadvantages associated with such cleaning compositions. For example, fluoride-containing compositions can dissolve stainless steel and other ferrous alloy equipment commonly utilized in vessel cleaning lines, and hydrofluoric acid and fluorides present in aging cleaning baths and rinse waters can - poses environmental problems in the disposal of

Compositions and methods for low-temperature cleaning of aluminum surfaces are disclosed in U.S. Pat.
bert Er1c B1nn5), U.S. Patent No. 41
No. 24407 (published November 7, 1978, Robe
r tEric B1nn5), U.S. Patent No. 3969
No. 135 (published July 13, 1976, Peter
F., King) et al. These patents disclose cleaning compositions containing sulfuric acid, hydrofluoric acid or fluoride salts, and surfactants.

Compositions and methods for high temperature cleaning of aluminum surfaces are disclosed in numerous patents, exemplified by U.S. Pat.
No. 35826 (published January 18, 1972, Andre
w J, Hamilton). Such high temperature compositions and methods are currently rarely used due to rising energy costs.

This time, the aluminum surface is acid-cleaned at a relatively low temperature.
Compositions and methods have been discovered that do not contain hydrofluoric acid and other fluorides.

The cleaning aqueous solution of the present invention contains the following components at the following concentrations.

Component f/l (solution) (1)
H3PO2 (No O%) About 3-22, preferably about 9-22, more preferably about 10-20 (2) H2SO4 (100%) About 4-24, preferably 6-15 (3) Surfactant About 0.1 to 7.5, preferably 0.5 to 2 The above wide range of phosphoric acid concentration in the cleaning aqueous solution of the present invention is 3
Although concentrations as low as Vl, but below the lower end of the preferred range (i.e., phosphoric acid concentrations of about 3 to 9 Vl), provide a consistent cleaning solution that can be operated at all commercial line speeds and operating temperatures. It is to be understood that these materials cannot be manufactured in a single manner and are not always useful in the practice of the present invention. Therefore, the preferred range of about 9 to 22 Vl of phosphoric acid is highly preferred in practice for producing commercially useful cleaning solutions that can be used in the wide range of operating conditions described below for the process of the invention.

Regarding the surfactant used in this aqueous cleaning solution, it may be an anionic, cationic or nonionic surfactant.

Specific examples of surfactants that can be used are as follows.

TERGITOL ANIONIC-08 (Union
Carbide Cor-porat 1on)2
- Anionic surfactant TRITON DF-16 (Roh
m & Haas Co,) a nonionic surfactant believed to be a modified polyethoxylated linear alcohol.
Corp.) Nonionic surfactant believed to be a modified polyethoxylated linear alcohol 51) RF'0NICLF-17 (Jef fer
PLURAFACRA-30 (BASF Wyando), a nonionic surfactant believed to be an alkyl polyethoxylated ether;
tte Corp.) A nonionic surfactant believed to be a modified oxyethylated linear alcohol.

PLURAFA CD-25 (BASF Wyando
tte Corp.) A nonionic surfactant believed to be a modified oxyethylated linear alcohol.

TRITON XX-102 (Roh k Haas
Coo,) Octylphenoxypolyethoxyethanol A trusted nonionic surfactant.

ANTAROX BL 330 (GAF Corp,)
TRITON CF-10 (Rohm & Haa), a nonionic surfactant believed to be alkylpoly(ethyleneoxy)ethanol
SURFACrANT ARl 50 (Hercul), a nonionic surfactant believed to be an alkylaryl polyether with about 14 carbon chains and about 16 moles of ethoxylation;
e* Inc.) nonionic surfactant PLURONICLO 61 (BASF Wyandot) believed to be an ethoxylated abietic acid derivative with about 15 moles of ethoxylation.
te Inc) ANTAROX LF-330 (GAFCorp, ) T, a nonionic surfactant believed to be a condensate having only chains of ethylene oxide and propylene oxide.
Nonionic surfactant PEGO5PER5E 700-To (Gly
c o Chemicals Inc.) approx. 14-16
Nonionic surfactant believed to be abietic acid ester with molar ethoxylation ICEPAL CA-630 (GAF orp,) Nonionic surfactant believed to be furkylphenoxypoly(ethyleneoxy)ethanol - TRYCOL LF-1 (Emery Indus
RENEX 20 (1, C0I, United 5) is a nonionic surfactant believed to be an alkyl polyether.
tates Inc.) 7-ionic polyoxyethylene esters of mixed fatty acids and resin acids The surfactant used in the aqueous cleaning solution of the present invention may be a combination of two or more surfactants. In fact, it is preferred to use the following combination in the cleaning solution:

(about 0.25-1.0, preferably about 0.40-0.
8θμ high detergency surfactant and (i) about 0.25 to 1.0, preferably about 0.40 to 0
．． 75 f/l low foaming surfactant The high detergency surfactant used in the above preferred surfactant combinations was tested in the Hard Surface Cleaning Test (M, N).

Fineman, ASTM Bulletin No.
, 192.49-55Q, September 1953) may be anionic, cationic or nonionic surfactants which give results of at least 90% on stainless steel. Examples of high-detergency surfactants that do
25, TRI'lυN X -102,5 [JRFA
CTANr AR150, Ni, Hi IGEPAL CA
-60 is mentioned.

The low foaming surfactant used in the above preferred surfactant combinations is the well-known Ross-
Any anionic, cationic or nonionic surfactant may be used which gives a foam of up to 20 m after standing for 5 minutes in the Miles Foam Test. Examples of such low foaming surfactants: Toshiteha, TR
ITON DF-16, POLYrERGENrS-5
Q5.5URFONICLF-17, ANTAROXB
L330, TRITON C:F-10, pLURoN
xcL061, ANTAROX LF-330, MIR
AWET B (Miranol Chemical
Co, , 2-butoxyethoxysodium acetate) MIN-FOAM IX (LJnion Car
bide Cc)rp, , a nonionic surfactant believed to be an alkyloxy (polyethyleneoxypropyleneoxyisopropanol) with a molecular weight of about 706)
can be mentioned.

Where a particular surfactant alone satisfies both the high detergency and low foaming criteria of a preferred surfactant combination, such surfactant alone may be present in an amount of about 0.5 to 2.0 V'l. This is a preferred embodiment of the present invention.

The amounts of phosphoric acid and sulfuric acid used in forming the cleaning aqueous solution of the present invention are given as 100% acids, but are less than 75% Ha P
It is convenient and common to add common commercial forms such as O4 and 66° Baume H2S O4 to form the concentrates and baths of the present invention.

The cleaning solutions of the present invention are conveniently formed by diluting a concentrated composition containing each component in water. Concentrated compositions which can be used for this purpose and which form part of the present invention contain the above components in concentrated aqueous solution. Each component is present in the concentrate in an amount sufficient to provide the required amount in the cleaning solution resulting from dilution of the concentrate with a controlled amount of water.

The concentrates of the present invention are stable over a wide range of temperatures and can therefore be transported and stored even under extreme winter and summer temperatures. Additionally, the concentrates of the present invention can contain all the components necessary to form the cleaning solution, unlike fluoride-containing cleaning solutions where the addition of hydrofluoric acid to the concentrate is impractical. can. The hydrofluoric acid components used in previously known methods usually have to be added separately under controlled and metered conditions, requiring extra steps and expense to form the cleaning solution.

The method of the invention consists of contacting the surface of the aluminum or aluminum alloy to be cleaned with the aqueous cleaning solution of the invention using any contacting technique known in the art, such as conventional spraying or dipping techniques. The temperature of the cleaning solution is preferably maintained in the range of about 115-140°F, although temperatures as low as about 90°F can be employed. The treatment time with the cleaning solution is usually about 10 seconds to about 2 minutes, preferably about 30 seconds to about 1 minute.

Following the cleaning step, the aluminum surface is rinsed with water to remove the cleaning solution. The aluminum surface may then be treated with coating solutions or dry finish coating compositions well known in the art. Also, pre-rinsing the aluminum surface with water before the cleaning step is sometimes beneficial to reduce the amount of contaminants entering the cleaning bath.

The use of the cleaning solution of the invention in the method of the invention provides a number of useful advantages. For example, as mentioned above, the compositions of the present invention do not contain fluorides, which have problems including handling, corrosion of metal equipment, and disposal; the process of the present invention is a relatively low temperature process, resulting in reduced operating costs; Provides fuel protection.

The compositions of the present invention also provide aluminum surfaces with unusually high gloss, which is a unique advantage for certain container customers when a marbled appearance is desired through container labeling.

The compositions of the present invention provide this superior gloss due to the lower rate of aluminum dissolution compared to previously known fluoride-containing compositions.

Additionally, the composition of the present invention provides a clean aluminum can without dome contamination.

In addition, the compositions of the present invention provide superior lubricant removal performance, resulting in water-tight aluminum containers.

Another advantage of the compositions of the present invention is that they maintain the aluminum dissolved in solution so that no sludge is formed in the cleaning bath. Also, since no precipitate is formed in the rinsing water tank, the problem of scale formation that often occurs when using conventionally known compositions can be eliminated.

The following examples are illustrative of the invention, but are not meant to be limiting.

Example 1 An aqueous concentrate was prepared containing the following ingredients and amounts.

Ingredients Amount H2
S04 (66° Baume) 243.
9 PH3PO4 (75%) 7
08 yS[JRFACTANT AR-15020
,3ySURFONICL,F-1713,OF water
Appropriate amounts of the above concentrated liquid were clear and stable.

The resulting solution was stirred to make it homogeneous.

The resulting cleaning solution had the following composition:

H2S04 (100%) 7,031!
/lH3P04 (100%) 15.9
41iE/IS [JRFACTANT AR-1500
,61y/l! 5URFONICLF-170, 3004 alloy aluminum cans drawn into 39 g/l single piece containers were used for this process. The can was covered with squeeze oil.

Five specimens were processed as follows.

(a) Spray treatment for 20 seconds with the above cleaning solution maintained at 130°F. (b) Water rinse by immersion in cold water for 30 seconds.
) After being left for 30 seconds, the test cans for appearance and drainage on both the inside and outside surfaces showed no drainage, no marbling, and a very high gloss. This can was suitable for further commercial processing. Five additional cans were processed as above, except that the spray time of step (a) was 40 seconds, averaging 5.5 square inches from each color surface having a surface area of about 120 square inches. The same results were obtained, except that an average of 62 η of aluminum was dissolved from the surface of the can. ~ Five more cans were treated in the same manner as above, except that the spray time in step (a) was 60 seconds, and the same results were obtained, except for the average aluminum dissolved perspiration value of 11.1 ■.

Example 2 The same concentrate used in Example 1 was made into a 4% concentrate/96
% water and the resulting solution was stirred to homogeneity.

The resulting cleaning solution had the following composition:

H2S04 (100%) 9.31/
/H3P04 (1-00%) 21.
25g/1SURFACTANT AR-1500,8
15i'//S[JRFONICLF-170,527
/l Aluminum cans were treated according to the method of Example 1 using the cleaning solution described above. The can was completely drained, free of marbling and had a very high gloss. The cans were suitable for further commercial processing.

The average aluminum dissolution values were as follows.

Souffle 1 hour (seconds) Amount of aluminum dissolved (■) 2
0 6.1 40 8.0 60 11.1 Example 3 1000 gallons of a cleaning solution with competing concentrations of the following ingredients was prepared.

Ingredients g/jH
2S04 (66° Baume) 12.
4H3PO4 (75%) 13.6 SURFACTANT AR-1500,82SUR
FONICLF-170,52 3004 alloy aluminum cans drawn into single-piece containers and covered with drawing oil were processed in a commercial cleaning line using the following procedure.

(a) l Spray treatment for 22 seconds with the above cleaning solution maintained at 36° F. (b) Rinse treatment 7 with cold water spray for 10 seconds (C)
Depositing a phosphate film on the can by spraying a standard chemical treatment solution (ALODINE 404 in water (2% by volume)) at 100°F for approximately 20 seconds (d) rinsing by spraying with cold water for 10 seconds (e) Rinsing with a 10 second spray of deionized water (f) Drying in an oven at approximately 300°F (g) Inking (labeling) the outside of the can and lacquering the inside The cans were tested using standard industrial contact cleaning tests ( TR-4 test) and all the cans passed this test, demonstrating their suitability for commercial use.

The cans had a high gloss and showed no marbling appearance through labeling.

Example 4 A cleaning solution was prepared with the following composition.

H2S04 (100chi) 4.39!
/lH3P04 (100%) 15.94
/1PLURAFACD-250,61F//TRI
A 3004 alloy aluminum can coated with TON DF-160, 39 g/1 drawing oil was subjected to the method of Example 1, except that the cleaning solution spray (step a) was sprayed for one hour and at the following temperatures: The following aluminum dissolution results were obtained by using the above bath.

20 130 5.8760
130 10.0720 14
0 6.9760 140
12.20 cans were completely dry and had a high gloss and no marbling. The cans were suitable for further commercial processing.

Patent applicant: Amkem Products Incorporated Patent attorney Aoyama Aoyama (1 other person)

Claims (1)

Claims: 1. Aluminum containing about 4 to 249 Vl of sulfuric acid, about 3 to 22 Vl of orthophosphoric acid and about 0.1 to 7.5 Vl of surfactant. Aqueous cleaning solution for base surfaces. 2. The above item 1, wherein the surfactant is a combination of a high detergency surfactant of about 0.25 to 1.09 Vl and a low foaming surfactant of about 0.25 to 1.0 Vl. Cleaning aqueous solution. 3. An aqueous cleaning solution for aluminum-based surfaces comprising about 4 to 24 mq of sulfuric acid, about 9 to 22 V of orthophosphoric acid, and about 0.1 to 7.5 Vl of surfactant. 4. Item 3 above, wherein the surfactant is a combination of a high detergency surfactant of about 0.25 to 1.0 fj/l and a low foaming surfactant of about 0.25 to 1.0 V/l. cleaning aqueous solution. 5. Sulfuric acid is about 6~l 5 t/I! The third above exists in
Or the cleaning aqueous solution in Section 4. 6. The above first 3 in which phosphoric acid is present at about lθ~20 Vl
Or the cleaning aqueous solution in Section 4. 7. High detergency surfactant is approximately 0.40-0.80 f/
4. The aqueous cleaning composition of paragraph 4 above, present at 1. 8. Low foaming surfactant is about 0°40-0.75'i/
The aqueous cleaning composition of paragraph 4 above, present in 1. 9. The aqueous cleaning composition of paragraph 4 above, wherein the high detergency surfactant provides a result of at least 90% in a hard surface cleaning test on stainless steel. 10. Low foaming surfactant R□55-Ml at 50°C
The aqueous cleaning composition of item 4 above, which has a foam of 20 rrn or less after standing for 5 minutes in the LES foaming test. 11. The aqueous cleaning composition of item 4 above, wherein the high detergency surfactant is an ethoxylated abietic acid derivative having about 15 moles of ethoxylation. 12. The low foaming surfactant is an alkyl polyethoxylated surfactant. The aqueous cleaning composition of item 4 above, which is an ether. 13. A concentrated composition for use in formulating an aqueous cleaning solution for aluminum-based surfaces, characterized in that it contains an aqueous mixture of the following components: (a) sulfuric acid, (b) orthophosphoric acid, and (C) surfactant (the above components can be used depending on the dilution of the concentrated composition with water, such as sulfuric acid concentration of about 4 to 24'il/l, orthophosphoric acid concentration of about 9 to
22' i/l and surfactant concentration approximately 0.1 = 7
present in the concentrated composition in an amount sufficient to produce a 5 Vl aluminum cleaning solution. ) 14. Surfactant or about 0.25 to 1.0 Vl (7) Produce a solution containing a high detergency surfactant and a low foaming surfactant of about 0.25 to 1.0 Vl by dilution. The concentrated composition of paragraph 13 above, which is a combination of surfactants present in an amount sufficient to. 15. The concentrated composition of paragraph 13 or 14 above, wherein the sulfuric acid is present in an amount sufficient to produce a cleaning solution containing about 6 to 15 f/l of sulfuric acid by dilution with water. 16. The concentrated composition of paragraph 13 or 14, wherein the phosphoric acid is present in an amount sufficient to produce a cleaning solution containing about lθ to 20 Vl of phosphoric acid upon dilution with water. 17. The high detergency surfactant has approximately 0.4 (1-0,
18. The concentrated composition of paragraph 14, above, present in an amount sufficient to produce a cleaning solution containing 8" o y7i by dilution with water. 18. -0.75
15. The concentrated composition of paragraph 14 above, present in an amount sufficient to produce a cleaning solution containing G/j by dilution with water. 19. The concentrated composition of paragraph 17 above, wherein the high detergency surfactant provides a result of at least 90% in a hard surface cleaning test on stainless steel. 20, low foaming surfactant is Ro s 5 in so'c
- 20I+ after standing for 5 minutes in the Ml les foaming test
The concentrated composition of item 18 above having a foam of II+1 or less. 21. The concentrated composition of item 17 above, wherein the high detergency surfactant is an ethoxylated abietic acid derivative having about 15 moles of ethoxylation. 22. The concentrated composition of item 18 above, wherein the low foaming surfactant is an alkyl polyethoxylated ether. 23, (a) surface as above No. 1.2.3.4.7.8.9
．． Contact with the washing aqueous solution of 1O111 or 12, (
b) A method for cleaning aluminum-based surfaces, characterized in that it comprises the steps of rinsing the surface and removing the cleaning solution therefrom. U. The method of paragraph 23 above, wherein the aluminum-based surface is contacted with an aqueous cleaning solution by spraying the solution. 25. The method of paragraph 23 above, wherein the solution temperature is maintained in the range of about 115-14.0"F. 26. The method of paragraph 23 above, wherein the aluminum base surface is the surface of an aluminum base can. 27. ( A method for cleaning an aluminum-based surface, comprising the steps of: a) contacting the surface with the aqueous cleaning solution of item 5 above, and (b) rinsing the surface to remove the cleaning solution from it. 28. (a) Surface A method for cleaning an aluminum base surface, comprising the steps of: (b) rinsing the surface to remove the cleaning solution from the surface; and (b) rinsing the surface to remove the cleaning solution.