JPS58185781A - Fluoride-free blend for deterging aluminum and method therefor - 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 broadly relates to techniques for cleaning aluminum surfaces;
In particular, it relates to the cleaning of squeezes of the type used for food and beverage t-packing and rounding, and ironed aluminum trough bodies. The container body or can can be effectively treated through the following processing steps to provide satisfactory corrosion protection and lacquer and ink [IR] properties, while still retaining the shiny metallic aluminum appearance of the container. In order to do this, this mill was used to remove residual hooking and drawing agents from the aluminum surface, as well as any gold particles, commonly referred to as smut, generated during the shaping operation. In the past, numerous acidic and alkaline cleaning formulation bath solutions have been used or proposed.

Among various cleaning formulations and water bath liquids, conventionally used
H Rui was proposed and the US axis needle No. 3.969,1
No. 35, @4,009,115 and No. 4,116,
No. 853. In this prior art cleaning formulation, fluoride ions are used as an essential or preferred ingredient to promote chemical attack on the aluminum surface to be cleaned, so that the surface is exposed during the forming operation. The resulting metal particles can be de-smutted and treated at moderate temperatures of approximately 120"F (49"F) without sacrificing the bright, shiny appearance of the aluminum.
℃) to about 140″F (60°C: ) to achieve the desired etching of the gold StZ surface. and the effectiveness of heptadide ion for removal.

While this results in energy savings when compared to cleaning agents that operate at temperatures above 1 soy (approx. It started to get unpopular from a certain point of view. There therefore continues to be a need to provide cleaning formulations that do not contain fluoride ions, while maintaining the commercially beneficial cleaning properties of prior art aluminum gauze compositions of this type. Historically, this woodcutter's aluminum cleaning formulation has been tested at around 100°C (38°C).
) to about 1607° C. (71° C.) to provide satisfactory cleaning within an industrially acceptable time, thereby providing relatively low temperatures of about 180° F′ or higher. One advantage is that substantial savings in energy costs can be achieved over lIb1! operated cleaning agents.

The advantages and effects of the present invention are achieved by an improved fluoride-free acidic cleaning formulation bath solution which is suitable for use at temperatures as low as 100'F to 140''Fs. The aqueous formulation can be used effectively and the aqueous formulation effectively removes skin stains and smut from aluminum surfaces within an industrially satisfactory time, thereby making it possible for the woodcutter to The cleaning agent formulation of the present invention, which renders the surface suitable for subsequent processing in conventional Tani manufacturing methods, is further advantageous in terms of reasonable cost, simple processing, effective performance, and relative to the prior art. It is named after % for overcoming the pollution problems associated with fluoride-containing shampoo fluids.

The advantages and advantages of the present invention are that the formulation characteristics include controlled effective amounts of surfactants or combinations of surfactants, sulfate ions, phosphate ions, and less than about 2 acid This is accomplished by an acidic cleaning formulation water bath containing an amount of hydrogen ions. More specifically, the aqueous cleaning formulation solution has a volume of about 0.1 to about 3 liters.
surfactant or modification I in amounts up to 0g C9/l)
Combinations of 11[l active agents and from about 2 to about 100
fiJ, phosphate ion in the amount of # and (iill
The mixture with salt ions is comprised of about 30 to about 80 g of phosphorus salt ions, and about 1 to 2 m, preferably about 0.5 to about 1.2 m. And I'm especially satisfied! - Contains hydrogen ions that give rise to 0.8. According to a preferred embodiment of the present invention, the surfactant contains a general
Hydrocarbon-based obstruction shown by Of')llIO)1
The surfactant and the abietic acid trout conductive surfactant represented by the general formula A(lt'0), H have approximately equal mt. The combination was made according to the description given in

The acidic cleaning formulation water bath solution is a controlled mixture of a surfactant in an amount up to about 200971, phosphate ions and 4i1 salt ions in an amount up to about 500F, #.

and - consisting of the above-mentioned active ingredients bearing aqueous ions that yield less than about 0 - can be easily prepared and supplemented by using a common solution.

During the standby process of the method of the invention, the aluminum surface to be cleaned has a common operating strength τ, preferably iJ l l O″ii' (43°C) from energy conservation considerations.
at a temperature of from about 140″F to about 10 seconds or more to about 5 minutes;
Contact with the acidic cleaning formulation water bath solution for up to 1 or more minutes, although a period of less than about 2 minutes is generally sufficient. In addition, while the water bath liquid is suitable for soaking and flushing, the shape of the aluminum container body suggests that it can be washed with a conventional spray device and then rinsed immediately after bathing. It is preferable to apply the solution and treat it with a bath solution.

Other advantages and effects of the present invention are described below in connection with the specific examples and preferred embodiments! elil! It will become clear by looking at this.

The &&Th procedure for forming an aluminum container body or can has conventionally been constructed as follows. That is, an aluminum strip is prepared, which is passed through a cupping press to form a preliminary cup-shaped inner plate, and transferred to a drawing and ironing press to produce an elongated cup-shaped body. During the molding press and drawing and ironing operations, a cooling liquid containing an organic lubricant, water or a dilutable emulsion is applied to the facing parts to facilitate the molding operation. Thereafter, the container body 1+ transfers the can to a trimmer, where its top end is trimmed. The trimmed material then passes through a washer that includes multiple washing, rinsing and processing stages. At the end of the cleaning and processing cycle.

The treated round cans are placed in a drying oven and the inner and outer surfaces (3) of the cans are subjected to multiple lacquering steps and external pattern printing h'. Typically, a pattern ink print is first applied to the outside of a can with appropriate markings, and after drying, this is followed by a conventional lacquer application on the outside of the can (3) and a process of approximately 10 minutes in the Kikunfun air open. ,]I! The coating is cured by heating to an ambient temperature of, for example, about 400"F'(204C)'. After cooling the can, the lacquer is applied to the interior surface of the can, and in this case the lacquer is not conventionally used. The inner lacquer coating 11i may include any type of lacquer coating 11i selected to provide chemical resistance to the food tfcUIIK material placed in the can at the next filling station.
Let it harden at a warm temperature, and add 21 g/1 liter of sugar to the 7th can:
The external lacquer coating of I may optionally be removed and subsequently subjected to an additional softening step prior to slm to the Nine Station.

Filled cans are often pasteurized to eliminate TL11-resistant bacteria. This pasteurized tin layer typically involves immersing the filled and sealed cans in water heated to between 9 and 160 degrees for about 30 minutes. Toshi's low II sterilization treatment does not affect the excess fest of the can] 1! Clothed 1111Il does not have any effect on 1111Il, but the external bottom surface of the container without fest is often exposed to extremely aggressive low temperatures. Simulates discoloration during sterilization.

In order to guarantee the excellent quality and durability of this type of delivered, face-coated and filled cans during processing, transport, storage and final use, not only in terms of their appearance but also in their durability, various tests are carried out on one can. surface lacquer paint vli
It was devised for the purpose of measuring adhesion, corrosion resistance at 71B temperature and high humidity, corrosion resistance of can surroundings, and discoloration of face painting and unpainted outer surface under various conditions. Remove dirt*@trade on the can surface and make the fit 1 more susceptible to subsequent processing and lacquering.If the cleaning of the can surface is one step in the manufacturing order, then the cleaned can surface should be cleaned. It is clear that this woodcutter's post-processing work is being neglected. Typically.

The can body that has been trimmed by the trimming operation is placed in a washing machine, where the can body is exposed to the cleaning agent of the present invention during preliminary cleaning. Sprayed for about 1 minute at a temperature in the range of 1407 to 150°C, the cans made by Kosou and then washed
The can body to be cleaned and rinsed is then rinsed with water spray at approximately 120"F for 2 seconds. The round can body to be cleaned and rinsed is then subjected to various types of treatments known in the art to improve its surface properties. and increase corrosion resistance as well as other Pfr properties.The treated cans are then re-sprayed with water at about 1,200 liters, followed by 15 minutes at 1'W, temperature (70
Deionized and on-water spray rinse at 80°F to 80″F.

Historically, the cans are dried in a hot air cycle oven for 5 minutes, generally at about 380' to 400'F. One can of cold brew is painted and lacquered as previously described.

The formulations of the present invention have been shown to provide effective cleaning and preconditioning of aluminum cans in a cleaning agent that does not contain any of the heptafide ion activators. The aqueous cleaning formulation according to the present invention contains a surfactant or combination of surfactants from about 0.1 to about 301/l, preferably from about 0.5 to about 1 og7t/l.
It contains an amount of The time-based surfactant or combination of surfactants used depends to the extent on the type of organic and inorganic contaminants present on the can surfaces to be cleaned, and is suitable for optimal cleaning of this type of soil. It is possible to make a passage to remove 't=J. Surfactants that can be used satisfactorily include anionic, cationic, or nonionic surfactants. Representative examples of this type of surfactant include the following.

That is, those raids
8J (Union, Carbide, Corporation) [2
- Anionic surfactant thought to be sodium ethylhexyl sulfate], "Triton L) F-16J (ROHM, AND, HAS.

Campa=-) Nonionic surfactant considered to be a Cf polyethoxylated linear alcohol], “Polytardient S-5051, FJ (Olin, Corporation 7)
Nonionic mrQ property agent thought to be a Cf polyethoxylated linear alcohol], [Sul7 Onyk LF-1
7J (J7 Ann, Chemical, Company) [Nonionic surfactant believed to be an alkyl polyethoxylated ether, [Plurafac® Mu-30J (BA
SF Wyandotte.

Corporation) [Modified oxyethylated [nonionic surfactant thought to be a chain furcoal], [h-light yX
-102J (ROHM, AND, HAS, KAN HONEY) [
Octylphenoxyborie)=? Nonimen world 1ki considered to be Jetanor? 'E'i agent], [Pluronic L61 J (BASF Wyandot, Inc.) [nonionic surfactant, and this appears to be a ring containing only ethylene oxide and propylene oxide. ], [Renex 20J (1, C
, I, United, Steen, Inc.) [A nonionic, polyoxyethylene ester consisting of Torahi Fattauta and Shinzouken.

According to an advantageous embodiment of the present invention, the surfactant comprises a mixture of a reconstituted water conductor surfactant and an abietin derivative mediated surfactant present in approximately equal proportions. is preferred.

Preferably, the hydrocarbon cast conductor used in the cleaning agent has the general formula: a divalent group selected from the combination, and n is a number from 7 to 22). The desired concentration of the surfactant is determined by the lower limit depending on the hardness of the washed sand, while the upper limit is determined by the stability of the surfactant in the aqueous acidic detergent solution. A range of about 1 to about 30 II/lt or more is suitable, a range of about 0.5 to about 2.17771 is preferred, and a *storm% of about 1.3 fi/l is preferred. has been found. Commercially available surfactants that may fit the general formula above include Triton CF-1 from Rohm, &, No.
0J.

[Antarox BL-] from GAF Corporation
330J and [Igebor CA-630J, from Emery Industries, Inc.]
Tricor LF-IJ, and 1 Pulla 7 AtkD from BASF Wyandotte, Corporation
There is -25J. These surfactants contain alkyl and alkylaryl R groups and fropoxy R' groups with n values ranging from 8 to 16.

The conductive surfactant excluding a and ethyne is represented by the general formula: % formula % (wherein R' and n are the same as above, and A is an abietic acid group). The abietin derivative surfactant works in conjunction with a hydrocarbon-based 94 extracorporeal surfactant to eliminate all types of aJ-capable organic contaminants that remain on the surface following the energized P6 temperature molding operation. There is something to remove.

The desired concentration range is 1gl1l of hydrocarbon water! This is Notooka in the I conductor field (3) activator. Commercially available! NTH activators include Surfactant ARI 50J, supplied by No-Curies, Inc. VC, and Vegospurs 700-TOJ, supplied by Glyco, Chemicals, Inc. Both of these commercially available surfactants serve as a source of abietic acid ester containing about 14 to 16 moles of ethoxide. Changes in the alkylene oxide terminal groups of any of the above surfactants should not adversely affect the effectiveness of the active agent; the last hydroxy group may be replaced by, for example, a chloride substituent. Alkyl or aryl substitutions may also be made.

In addition to surfactants, detergent formulations are essential ingredients
I! Contains about 2 to about 100g/Σ
'l, preferably present in an amount of from about 5 to about 3517t, and (iii & salt ions).
Preferably, it comprises from about 30 to about 80 kk- of the total weight of 1 chloride ions.

If the alkali metal phosphate ion beam is used, it can be introduced in one of a number of baths that are compatible with the phosphorus ammonium salt. Motsu and phosphorus also constitute preferred woods.

As in the case of phosphate ions, the sulfur salt ion itself also constitutes a preferred material, but the il# salt ion can be used in any of a number of baths that are compatible with salts, including alkali metal and ammonium salts. It is possible to interrogate in this way. In either case, phosphate and sulfate ions are introduced to less than -2, preferably about 0
．． It is preferred to provide a hydrogen ion linearity that also reduces the lIf of the cleaning agent formulation used to have a value of between 5 and about 1.2, sometimes satisfactory at about 0.8. Excessive woody ionicity of rounding resulting in the desired acidity can be conveniently achieved by appropriate additions of phosphoric and sulfuric acids.

This addition necessarily introduces Li1c phosphate and sulfate ions simultaneously into the liquid preparation.

When a clear shiny aluminum appearance is required, combine 1 phosphate ion and 6 salt ion 1I
111Lt - preferably less than about 1777/1. If the aluminum surface condition is white, etched or can be chemically resistant as in the case of whole-painted or painted applications, the combined degree of phosphate and sulfate ions will be about ioog. /zVCt. Since the effectiveness of cleaning and etching aluminum surfaces is related to the time, temperature and acidity of the cleaning process, the concentration of the active ingredient can be increased for any given situation. Adjustments can be made within the parameters defined hereinabove to achieve the desired cleaning and appearance of the aluminum surface.

According to a feature of the method of the invention, the aqueous solution of a hostile cleaning formulation is applied to the aluminum surface to be cleaned.

It can be applied by dipping or fiL coating, but it is preferable to use spray coating scissors depending on the shape of the container. The cleaning agent bath solution is applied at a temperature of one storm in the range from about 100° to about 16,071°C, but from an energy conservation perspective about 110°
Preferably, the coating is applied at a temperature of from about 140F. The contact time of the cleaning agent with the aluminum surface will vary depending on the size and nature of the contaminants present on the surface, and typically ranges from about 10 seconds to about 5 minutes, but most For conditions, the contact time is less than about 2 minutes, such as from about 30 seconds to about 1 minute.

If undesirable foaming occurs due to different application conditions for cleaning solutions, fk, particulate formulations may also be used. Optionally, any one of a number of commercially available antifoam agents may be included in conventional amounts.

The so-called TR-4J test method was developed to evaluate the resistance to discoloration of unlacquered aluminum surfaces after cleaning and processing, and to evaluate the resistance of aluminum cans during industrial pasteurization. The so-called "r* bird eating test" simulates dust exposure on the outside bottom of the paint. To this end, we simulated a typical aqueous formulation used in cryogenic processing containing 82.4 parts per million (ppm) of sodium chloride, 82.4 parts per million (ppm) of sodium carbonate, and deionized water. By doing this, the water wrinkle solution is made into ceramics. The water quality conditioner used is commercially available [Teubois 9]
15", was filled with 4 g of a product supplied by DuBois, Chemicals, Inc., which showed total alkalinity [5,8% NaOt-] and analyzed the amount of rice, sodium nitrate, sodium carbonate. , triethanolamine and dotecylphenyl polyethylene glycol. The test method using the TR-4 test profile described above is

And use a container that is not lacquered in the bath.

This involves a step of subjecting the specimen to a concrete 150'F soil while maintaining it at 5'F.Following this test, the test specimen is removed from the heat, rinsed with water, and dried. The test specimens are rated from 1 (no staining or discoloration) to 10 (ii golden to grayish color discoloration or mottled extensive surface heterogeneity). Bonito grades 1-4 are generally considered commercially acceptable in the aluminum can industry, whereas $lI&5-10 are considered acceptable.

Improved Fluoride-Free Cleaning Formulations and Methods of the Invention - Specific examples are provided below to further illustrate. These examples are shown for illustrative purposes only! A#1 I was raped once, and again ~ Hu #i
! As mentioned during the ice range.

It will be understood that it is not intended to delineate the scope of the invention.

Example 1 For comparison purposes, a hot acidic cleaning solution containing no 7 fluorides was prepared using sulfur @ (100%) 7.7! /l, Dik's K "^R-
Abietic acid derivative surfactant labeled as 150J about 21771. Made by containing about 2 fl/l of a hydrocarbon derivative surfactant commercially available under the designation Tricor LF-IJO, and the balance water. Total 1
9j wash solution is prepared as indicated - approx. 1.2. Aluminum cans from a single can trimming operation with residual lubricant and coolant remaining on the surface of the can are cleaned with a Susley Koso 9 cleaner for 91 minutes at a temperature of about 140''F.

The cleaned cans are then rinsed with tap water for 15 seconds at approximately 120 mL.

The cans that have been washed and rinsed are
Bonderei) sold under K-780JO, Hunker,
The sample was treated six times using a ROM-free treated water F# solution available from Barker, Degage, Inc., Glasnax, Inc., Chemicals. This place! The I bath solution is overused at -3.7 by spray painting for 15 seconds at a temperature of about 1207.

The treated round cans were subsequently rinsed with tap water at 120"F for 15 seconds, again with a spray water rinse and then with a spray deionized water rinse for 15 seconds, after which the cans were placed in a recirculating air open at 3801 for 5 seconds. Let dry for a minute.

The bottom of the can is removed as a test specimen and subjected to the TR-4g test according to the procedure described above. TR-4
At the conclusion of the test, inspection of the unlacquered exterior underside of the test specimen yielded a rating of approximately 10, 9, which is generally unacceptable commercially. At the completion of the cleaning process and before the chemical storm membrane treatment, no etching or water break was observed on the surface of the five cans.

Example 2 Washing [k
The aluminum cans were prepared and trimmed and processed in the same order as described in Example 1. Upon completion of the cleaning process, the surface of the can should be free of any etching and water break. TR on the bottom of the can
-4 test, the rating of 54 was confirmed.

Example 3 A cleaning solution was prepared as in Example 1, except that 9#/j of phosphoric acid (100%) was added, and the same order as in Examples 1 and 2 was applied to the trimmed aluminum cans. Process with. When the cleaning process is complete.

The surface of the can was etched to the desired degree, and no water break was observed.

The post-mortem can bottom S subjected to the TR-4 test showed a rating of o1.

This is commercially acceptable.

Example 4 The degree of phosphoric acid is 13.51! , ek, as described in Example 3, except that the @wrinkle of the area solution was decreased from 140″F to 130″Kthk.
#The water bath solution was v4at. The results obtained with lower temperature and higher phosphorous salt ion temperature are fruitful in Example 3.
The results were similar to those obtained for the treated test specimens.

The results of Examples 2 to 4 show that the synergistic effect of sulfate and phosphate ions in combination with surfactants removes organic contamination and metal smut, resulting in satisfactory cleaning and etching; clearly shows that it retains an attractive shiny metallic appearance without excessive etching.

Tests conducted using a similar solution in which 1911/l of hydrogen chloride Wk (100%) was added to the bath solution of Example 1 resulted in excessive etching on the surface of the can, resulting in streaks and discoloration. , an undesirable whitish appearance was obtained.

Furthermore, the results of the TR-4 test were unsatisfactory from an artistic point of view. Similarly, nitric acid 10.4% in the detergent formulation of 91i1
The 1/l' addition produced virtually no etching on the surface of the can, while the results of the TR-4 test were artistically unsatisfactory.

Replenishment or supplementary light for the operation of the number of washing water baths according to the present invention can be conveniently carried out by using the following concentrated M material. That is, the III condensate contains each of the basic components in appropriate proportions such that the appropriate chain degree of the working bath is obtained and maintained by dilution with water. The Iida linearity of the various components in this concentrate is
The extent to which this occurs depends on the stability and compatibility of each component at such high chain degrees. Conventionally, about 2o
Suitable for aqueous fluids containing a controlled mixture of phosphate ions and (jiwi, salt ions) up to about 500g// of surfactants up to og7T, to9, suitable for dilution with an appropriate amount of water. This provides a working cleaning solution of the desired degree of sophistication.

Preferred embodiments of the disclosed invention have been designed and designed to achieve the above objectives.

It will be understood that the present invention may be susceptible to forms, changes and modifications without departing from the reasonable spirit of its proper scope or scope.

Claims (8)

[Claims] (1) from about 0.1 to about 30p, #'f: at least 111N- of the external activator present, and of phosphate ions and WIk salt ions present in an amount of from about 2 to about 10077/l; a controlled mixture comprising from about 30 to about 80% by weight of phosphate ions as well as hydrogen ions present with an adversity of less than about 2%. Kotot
- an aqueous heptadide-free acidic formulation suitable for cleaning aluminum surfaces with % mold. 2. The formulation of claim 1, wherein said hydrogen ions are present in an amount of about 0.5 to about 1.2. (3) A formulation of 4 permissible formulations with a pre-water distribution ion yielding about 0.8 -. (4) The external active agent has a molecular weight of about 0.5 to about 10971.
The scope of patent claims that exist with the amount of money lol! A formulation of Section 1 formulation. (5) The formulation of claim 1, wherein the surfactant comprises a mixture of a carbonized woody e-conductor surfactant and an abietin # derivative surfactant. 6. The formulation of claim 1, wherein said mixture of phosphate and sulfate ions is present in an amount of about 5 to about 3 sy/l. (7) The formulation according to item 41) t'F seeking range $1, wherein the frozen confection ions are introduced as phosphoric acid, ranges and mixtures thereof. (8) a controlled mixture of phosphate and sulfate ions with up to about 20,077 liters of surfactant/l;
007F/F and its phosphate ion is about 3
0 to about 80 weight - 69. And hydrogen ions are PH0
%tF# present in an amount sufficient to reduce the *Acidic saw water #1g. 9) Clean the interior of the aluminum surface to be cleaned for a period of time sufficient to effect the desired cleaning and etching within the aluminum surface. A step of bringing the fluoride described in Section 4, Section 5, Section 6 or Section 7 into contact with an acidic compound bathing solution that does not contain water, and then a step of stopping contact between the aluminum surface and the hostile compound bathing solution. A method of cleaning an aluminum surface comprising: