JPS6040509B2 - Low temperature cleaner for metal surfaces - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for cleaning metal surfaces and a cleaning method;
More particularly, the present invention relates to an aqueous alkaline cleaning solution containing a corrosion inhibitor that prevents or inhibits etching of metal surfaces.

Although the present invention is described with respect to cleaning soiled tin surfaces with organic lubricants applied to tin-plated surfaces, such as tin cans, as a drawing aid during cold forming operations, it has wide applicability. It is something that you have. Cleaning is essential as a preliminary to many surface finishing operations.

It is usually required, for example, before corrosion protection treatment and before the application of organic finishes to the surface, and is particularly important in the case of metal surfaces where organic substances have been newly applied as an aid for cold forming. be. The above substances must be removed to obtain a surface suitable for organic or bran finishes, respectively. One example of the need for such cleaning is when manufacturing two-piece tin-plated pultruded ironing cans.

Due to the high cost of tin, an annular shape of tin-plated steel, generally with only a thin layer of tin plating, is first drawn and then passed through several dies to form a unitary structure of side walls and can bottom. Being squeezed. Cans produced by this method are generally characterized as thin-walled, thick-bottomed containers with uniform wall thickness. Such cans are referred to herein as DIJ (Draw and Iron) cans. The forming operation is facilitated and the die and metal surfaces are protected by applying lubricant to the tin plate surface during or prior to the forming operation. The lubricant applied to the tin surface generally consists of various kinds of nutritious or vegetable oils and heavy metal soaps.
Post-molding cleaning steps are important in a good manufacturing process, as it is desirable to have a clean surface to ensure the adhesion of subsequently applied sanitary lacquers and/or decorative varnishes. A significant problem with DI tin-plated containers is that the drawing operation stretches the tin plate surface, exposing portions of the base metal, which lead to corrosion.

The base metal may be a ferrous metal such as iron, an iron alloy, or various types of steel. The problem with tin plate cleaners is to obtain a cleaner that provides a water-tight surface without excessively etching the tin and promoting corrosion of the base metal. A water-tight surface is one that has been sufficiently removed from lubricants, dirt, and other contaminants to maintain a continuous film of water. Etching results from the chemical action of the cleaning agent on the tin surface, resulting in a rough, cloudy surface.

Additionally, etching removes some of the corrosion protective tin from the surface, reducing the anti-corrosion performance of the surface and exacerbating corrosion problems by exposing the base metal. Etching and/or corrosion are clearly undesirable when a smooth, shiny surface is desired, as in the case of beverage cans. Another problem with tin plate cleaners is that in lines where stopping the processing line after drawing, ironing and cleaning can expose the cleaned cans to the cleaner for extended periods of time, the cleaner has a protective effect against ambient conditions. It is not to have.

This prolonged exposure causes corrosion of the substrate surfaces exposed by stretching or etching, rendering the container unfit for use. In addition, surface corrosion or corrosion adversely affects the adhesion of the conversion coating or subsequently applied sanitary lacquer coating. Alkaline agents, such as aqueous solutions of alkali metal salts of silicic acid, phosphoric acid, carbonic acid, and boric acid, have been found to be most suitable for providing the desired water-tight surface; It has no neck orientation.

When certain compounds are added to an alkaline cleaning solution,
It has been found and proposed that it helps inhibit etching of tin surfaces under alkaline conditions. Conventionally, inhibitors such as chromic acid, dichromic acid, and to a lesser extent alkali metal salts of silicic acid have been added to the above-mentioned alkaline aqueous solutions to inhibit etching of the tin surface. The resulting cleaning agent is generally 1500F (65.6ko○)
Applicable at temperatures above. The action of alkaline substances on the tin surface is bidirectional, increasing as the pH increases.
Complete protection of the tin surface from etching is not always possible with such inhibitors, especially at pHs above about 1 a. Such detergents having a pH of about 12 or less have a lower tendency to act on the tin surface and therefore the known inhibitors are more effective; however, the cleaning capacity of such low pH detergents is generally lower and less effective for cleaning. It is necessary to treat the tin surface for a long time. In addition, the use of chromium compounds as inhibitors creates toxicity and industrial sewage problems that cause environmental problems. Numerous patents are directed to compositions and methods for cleaning tin surfaces.

The detergents disclosed in these patents are at least 1400 F (6
It is characterized as a high temperature cleaner since it is applied at a temperature of 0.0 qo). U.S. Patent No. 2,836,566 includes
Water-soluble steel salts selected from the group of alkali metal metasilicates, sulfates, chlorides, acetates and cyanides, 1,3-
Diaminoptan, monoethanolamine, 2-amino-
A tin surface cleaner composition is disclosed that uses an aqueous solution of an amine selected from the group of 2-methyl-1-propanol and triethanolamine, and soda ash in addition to water. This solution is about 11. It has a fence on the top. In one example, cleaning tin surfaces by immersion in a solution at boiling point for up to 15 minutes is disclosed.
This solution temperature and cleaning time is economically disadvantageous due to the energy required to maintain the cleaning solution at boiling point and the 18 minute soak time required for the cleaning liquid.

In addition, the need for copper salts containing cyanide steel adds to the cost of cleaning processes using this solution and makes it undesirable for applications such as beverage cans, as well as spoilage. provide a problem. Furthermore, when using solutions containing copper salts, there is a possibility that some copper will be plated onto the tin surface. This is a problem because copper looks different and a uniform, shiny tin surface is generally preferred by manufacturers purchasing cans for filling beverages, for example. No. 7, U.S. Patent No. 7, discloses a cleaning composition which, upon addition of water, forms an aqueous solution for cleaning tin-plated iron-based metal surfaces.

This aqueous solution contains a condensed phosphate selected from the group of alkali metal metasilicates, tripolyphosphates and pyrophosphates, and borax. Alkali metal metasilicates are said to increase the cleaning power of the solution and add protection to the surface from corrosion prior to conversion treatment.
The cleaning solution is approximately 150-1900F (65.6-87.
19 sand at a temperature of 8oC) is applied to the surface for about 1 minute.

Preferred temperatures are about 150-1700F (65.6-76
7℃). The pH is maintained in the range of about 9.0-10.15. All examples disclose solutions with a pH I below 0 and a temperature of at least 160 T (71.7° C.).
This solution has certain drawbacks, the main one being that the solution must be applied at temperatures above 1500 F (65.6 O), which consumes a lot of energy and therefore much less than with cleaners at much lower temperatures. This means that it requires a high cost to use. Additionally, both borates and phosphates present environmental concerns and thus create factory scale treatment problems. U.S. Pat. No. 4,094,701 discloses a method of cleaning tin surfaces that does not substantially etch the tin.

The method includes an alkaline component which may be an alkali metal borate, carbonate, phosphate, hydroxide, oxide, silicate or mixtures thereof, one or more surfactants, and an inhibitor. It consists of contacting the surface with an alkaline aqueous solution containing an organic tannin as an agent. The object to be cleaned is sprayed with the solution for about 1-2 minutes at a heated temperature. The pH of the detergent is at least 9, preferably 10-13 and most preferably 10-10.5. At high pH values, tannins are gradually inactivated. This patent states that when the detergent is adjusted to the preferred pH range, 140T (60.
0° C.) or higher. Accordingly, this patent discloses the cleaning agents disclosed therein as 1400
It teaches use at temperatures above F (60,000) and multiplication values of 9 to 10.5. This patent discloses that alkali metal borates and phosphates may be used.

Both borates and phosphates present environmental problems and therefore create industrial effluent treatment problems. This patent discloses a cleaning solution that may be used to clean tin surfaces without etching at temperatures below the boiling point for a time of no more than 2 minutes, but employing temperatures above 140 T (60.0 qo) is still economically disadvantageous. Therefore, without the use of components currently known to be environmentally problematic, significant cost savings are achieved, the potential for etching and corrosion during line stoppages is reduced, and energy consumption is reduced by up to 4. Etches tin at lower temperatures than previously employed effectively when applied for a time of about 1 minute or less and for a longer time than disclosed herein for use without etching. There remains a need for compositions that can be effectively used on tin surfaces to provide a water-tight surface without causing any damage.

It is therefore an object of the present invention to provide compositions, solutions and methods for cleaning tin surfaces, hakama sparrow metal surfaces, without the use of ingredients currently known to be environmentally problematic. , the surface is water-tight without etching the tin, and does so at lower temperatures than conventionally employed effectively.

The main object of the present invention is to provide a low-temperature alkaline aqueous solution for cleaning tin-plated metal surfaces so that the surface will not be etched or drained of tin.

Another object of the present invention is to provide a low temperature tin plated metal surface cleaning solution composition and method of use thereof to provide a water-tight surface without etching the tin.

In accordance with the present invention, an alkaline component is present in an amount effective to substantially remove dirt, lubricants or other contaminants from a tin surface, and substituted benzenes, quinones and The tin surface is visually cleaned by applying to the tin surface an aqueous alkaline cleaning solution having a pH of about 11-13 and containing an effective amount of an inhibitor selected from the group of substituted quinones to inhibit etching of the surface. A method is provided for cleaning a tin surface to substantially remove the contaminants from the tin surface without visible etching.

Also in accordance with the present invention, an alkaline component and quinones, substituted quinones and at least two hydroxyl substituents are present in an amount effective to substantially remove dirt, lubricants or other contaminants from the tin surface. Ortho position, para position,
said contamination without visibly etching the tin surface, comprising an inhibitor selected from the group of substituted benzenes in the meta position, symmetrical or asymmetrical arrangement, in an amount effective to inhibit etching of the surface; An aqueous cleaning solution having a pH of about 11-13 is provided for cleaning the tin surface to substantially remove material.

The alkaline components in cleaning solutions useful in the methods and compositions of the present invention may be compounds known in the art that provide alkaline solutions when dissolved in water.

Preferably, the alkaline component is used in the form of a compound selected from the group of alkali metal hydroxides, carbonates and silicates and ammonium hydroxides and carbonates or mixtures thereof. Particularly preferred alkaline components are sodium carbonate, sodium metasilicate,
and a mixture of compounds selected from the group of sodium hydroxide and potassium hydroxide. The alkaline component is present in the cleaning solution in an amount effective to substantially remove dirt, lubricants, or other such contaminants.

Generally, applying the solution at a higher temperature requires more alkaline component, and applying the solution at a lower temperature requires less. Preferably, the amount of alkaline component in the solution will be at least about 2 parts per night, and more preferably about 3 to 5 parts per night. Higher concentrations may be employed, but the effect obtained is usually not significant. The cleaning solution may typically have a pH value of about 11-13, about 12-12.
A pH value of 8 is preferred. This pH is measured at a solution temperature of about 270. Inhibitors of cleaning solutions useful in the method of the invention include:
Compounds selected from the group of substituted benzenes, quinones and substituted quinones having at least two hydroxy substituents; mixtures of inhibitors can also be used.

Representative examples of substituents on the benzene ring include, in addition to hydroxy, halo, alkyl, carboxy, nitro, cyano, and alkoxy. Such substituents are also typical examples of substituents for substituted quinones. Typical quinones and substituted quinones useful as inhibitors of the present invention include 1,2-penzoquinoso, 1,4-penzoquinone and formulas m [wherein R,, R2, R3 and R4 are hydrogen, alkyl, alkoxy, hydroxy, halo, nitro, cyano or carboxyl, or R, and R2 form an alkyljetyl group or together with the quinone ring to which they are attached naphthaquinone. form.

] Substituted quinones are included.

Typical adulteration benzene inhibitors of particular interest in the compositions of the present invention include catechol, resorcil, 1,4-dihydroquinone, 1,2,4-trihydroxybenzene, 1
,3,5-trihydroxybenzene and 1,2,4,
Included are polyhydroxybenzenes such as 5-tetrahydroxybenzene.

Preferred inhibitors for use in the method of the invention include 3,4
, 5-trihydroxybenzoic acid, 1,2,3-benzentriol and 1,4-benzenediol and 1,4
-Dihydroxybenzenes such as benzoquinone and quinones are included.

The inhibitor is added at an effective level to inhibit etching of the surface. Generally, as the concentration of alkaline components increases,
The required inhibitor concentration also increases. Also, as described below,
Soft water has a tendency to be more corrosive than hard water, so
When cleaning solutions are formulated with soft water, higher inhibitor concentrations are generally required than when formulated with hard water. The amount of inhibitor in the solution is at least about 0.02 μl/
It is preferred, and more preferably about 0.02 to 0.06 m/sleeve. Concentrations in excess of 0.06 μg/g can be effectively employed, but the resulting cost increase is usually not offset by significant etch inhibition.

The addition of polyelectrolytes to the cleaning solution of the present invention results in a solution that can be used effectively without the commonly experienced precipitation of calcium and magnesium ions that cause water hardness, regardless of the hardness of the water used to formulate the solution. Seen to be served and served.

Such precipitation is a problem, for example when spraying is selected as the method of use, as it results in precipitates clogging the spray nozzle. Polyelectrolytes are high molecular weight electrolytes of natural origin, such as proteins, or of synthetic origin, such as polymerized organic acids.

Since polyelectrolytes in solution do not dissociate and provide a uniform distribution of cations and anions similar to simple electrolytes, certain signal ions bind to polymer chains. Therefore, for example,
Negative charges may be in the polymer chain, with only the cations being free and diffusing through the solvent. Hardness is a property of water commonly used to describe the total concentration of calcium and magnesium ions.

Other polyvalent cations, rarely present in trace amounts or more, also contribute to hardness. Hardness is measured using American S ratio
TS for Testing aM Nterial
“Snenderd MethMs” published by s
ofTeStfor HbrdneSS in Wa
ter” D Eagle Signation DI126-67
It may be done by titration as shown in (Re-approved 197-Mu King). Hardness can be given in parts per million (ppm) of calcium carbonate equivalent. The higher this value, the
High hardness. Water hardness varies greatly from one industrial site to another. Generally, water having a hardness of about 10 pm or less may be considered soft water, whereas water having a hardness of about 10 pm or more may be considered soft water. In some coastal areas, the hardness is only about 50-low pm and increases to about 30 pm where the water flows through limestone deposits. In some locations in the Midwest, hardness is approximately 400-50 PM. Sedimentation is usually experienced to a large extent when water hardness increases. As hardness decreases, water becomes more corrosive. Therefore, polyelectrolytes are preferred, but optionally added to the cleaning solution of the present invention. When adding a polyelectrolyte, this may be a compound known in the art to prevent precipitation of minerals that are responsible for water hardness.

Certain advantages are realized by selecting polyelectrolytes that do not contain phosphates. Since phosphates are considered an environmental problem, it is an important advantage that the industrial effluent is free of phosphates. In addition, the traditionally used alkali metal tripolyphosphates have the deleterious effect of promoting etching or detining. Accordingly, preferred polyelectrolytes for use in the cleaning solutions of the present invention are polyelectrolytes such as GAF Gantrez S-95 and Rohma Chunichi AAS Tamol 960. These polymers do not promote detining and to some extent suppress etching. When adding a polyelectrolyte, it is preferably added in an amount effective to substantially prevent precipitation of calcium ions and magnesium ions, which are the main causes of water hardness.

Typically, higher amounts of polyelectrolyte are required when water hardness is higher than when water hardness is lower. Preferably, the amount of polyelectrolyte is at least about 0.1 m/s, more preferably 0.1 m/s.
~1 evening/sleeves. Although they may be present in the cleaning solution at concentrations of more than one night/day, generally higher concentrations do not provide significant improvement in the desired effect. Although it is not essential to add one or more surfactants to the aqueous alkaline cleaning solution of the present invention, it is preferred.

Additionally, when adding a surfactant that is not a low foaming surfactant, it may be desirable to add an antifoaming agent. Since seed foam presents a significant problem in practical operations, an antifoam agent is desirable where it would slow down or shut down the wash line. Although such materials enhance the performance of the cleaning solution, they are not an element of the invention since they are used to perform essentially the same function as previously known solutions. It has been found that the presence or absence of a surfactant has no significant effect insofar as the etching of the tin surface is promoted while being inhibited by the cleaning solution. Typical surfactants and wetting agents that can be used in cleaning solutions are ethoxylated linear alcohols and octyl or nonylphenoxy polyethoxyethanol.

Generally, /ionic surfactants are preferred because of their low foaming properties. When adding a surfactant, it is preferred that the cleaning solution contains at least 0.2 of the one or more surfactants.

A particularly preferred amount is about 0.2 to 0.5 m/sleeve. The tin surface is cleaned by contacting it with an aqueous alkaline cleaning solution of the present invention for a time and temperature effective to remove dirt, lubricants or other such surface contaminants from it without visibly etching it. It's okay to be.

Typically, the solution temperature is at least about 1000F (37.C
). The preferred range is about 100-1300F
(37.8 to Hiro.400), the more preferable range is about 11
5-1250F (46.1-51.70). The temperature employed tends to be higher for solutions with lower concentrations of alkaline components than for solutions with higher concentrations.

Therefore, the processing temperature may vary slightly in inverse proportion to the pH of the cleaning solution. Processing time may depend on the typical usage.

A preferred method of use is a spray method, with which the treatment time may be reduced as the spray pressure is increased. Spraying means currently known in the art are approximately 25 to 35 p.
Generally operating at a spray pressure of sl, a processing time of about 40 seconds to 1 minute is sufficient to provide a water-tight surface.
Spraying means with a pressure of 60 to 10 sl are known,
Currently not commonly used, effective processing times of about 1-5 seconds may be used. The spray method is just a typical example of a method of use. Any conventional means known in the art may be used to contact the tin-plated surface with the cleaning solution. The longer the interval between the manufacture of tin-plated metal products and their cleaning, the longer the processing time tends to be. For drawn and ironed tin-plated steel cans, intervals as small as 18 minutes can result in a significant increase in cleaning time. Additionally, processing times may vary depending on the type of lubricant used in the manufacturing process, with some types of lubricants being more easily removed than others. Application times of up to approximately 30 minutes were employed to determine the extent to which this cleaning solution suppresses tin etching, and it was determined that tin-plated surfaces may be contacted with this solution for up to approximately 30 minutes without etching the tin. It was done.

However, in practical cases, the shortest time effective to provide a water-tight surface for tin etching is the best time to apply the present composition to the tin surface to be cleaned in order to achieve maximum cost efficiency. It is predicted that the situation will be good. After treating the tin surface with the cleaning composition, the surface is typically rinsed with tap water at least once and then rinsed with deionized water;
Heating temperature, preferably about 350-4000F (176.
7-204.4°C). Thus, surprisingly, the present composition does not visibly etch tin when formulated with an aqueous alkaline cleaning solution and contacted with a tin-plated metal surface for about 30 minutes or so. Therefore, the present solution provides significantly increased protection against etching and corrosion over conventional solutions in the event of line outages or prolonged exposure to similar cleaning solutions. In addition, conventional solutions effectively clean tin surfaces to provide a water-tight surface without visibly etching the tin.
The present cleaning solution has temperatures as low as at least about 100°F (37.800°C), and preferably from about 100° to 13°F (37.8°C to 37.8°C), whereas the present cleaning solution requires temperatures of at least about 100°F (37.800°C) and above.
It can be effectively used at a temperature of 54.4 qC).
Significant savings in energy costs can therefore be realized through the use of the inventive solution, which provides a visibly etched, water-tight tin-plated surface over 400 F (22.0 F) over conventional solutions. It can be used effectively at temperatures as low as 0). The cleaning agent of the present invention may be formulated as an aqueous concentrate or solid cleaning composition in addition to water to provide an aqueous alkaline cleaning solution of the present invention.

As an aqueous concentrate, the cleaning agent will contain approximately 0.5 to 2
When added to water at a concentration of % by volume, it effectively removes dirt, lubricants or other contaminants from the tin surface without visibly etching the tin surface, even at low solution temperatures. pH of about 11-13 for cleaning
to provide an aqueous alkaline cleaning solution comprising an effective amount of an alkaline component to substantially remove said contaminants from a tin surface, and an effective amount of an inhibitor to inhibit etching of said surface. It is mixed.

The inhibitor is a compound as defined above. Preferably, the concentrate is added to the water at a concentration of about 1-2% by volume. Preferably, the alkaline component as defined above comprises up to about 770 ml per concentrated liquid, more preferably from about 250 to 250 ml per concentrated liquid per ml.
It can exist for 500 nights.

Preferably, the inhibitor may be present at least about 2 times per concentrate, and more preferably from about 2 to 6 times per concentrate. o The concentrate is optionally present in a polyelectrolyte and/or
Alternatively, it may contain one or more surfactants.

The polyelectrolyte defined above is preferably added in an amount effective to substantially prevent precipitation of calcium ions and magnesium ions, which are the main causes of water hardness, and more preferably about 10 to 20 hours per concentrated solution. You can add . As a solid cleaning composition, the cleaning agent comprises about 30% of the solid cleaning composition.
When added to water at ~7 tm/concentration, tin substantially removes dirt, lubricants or other contaminants from it without visibly etching the tin surface, even at low solution temperatures. Approximately 11-13 - to clean the surface
to provide an aqueous alkaline cleaning solution comprising an effective amount of an alkaline component to substantially remove said contaminants from the tin surface, and an amount of an inhibitor effective to inhibit etching of the nuclear surface. It is mixed.

The inhibitor is a compound as defined above. Preferably, the cleaning composition is added to the water at a concentration of about 4.6 to 6.7 hours per hour. Preferably, the alkaline component as defined above comprises at least about 15% by weight of the composition.

Preferably, the inhibitor comprises at least about 0.1% by weight of the composition. A particularly preferred concentration is about 0.5 of the composition.
~2% by weight. The composition as defined above may optionally contain
It is preferable to use an effective amount of polyhydric acid to substantially prevent the precipitation of calcium and magnesium ions, which are the main causes of water hardness, and the concentration is between 0 and 10% of the composition.
about 1% by weight of the composition, more preferably about 3-1% by weight of the composition.
% by weight.

The cleaning compositions may optionally contain, as diluents and the like, compounds characterized as inert with respect to possible positive or negative influence on the cleaning and non-etching properties of the cleaning solutions of the invention. A typical example of such a compound is sodium sulfate. Examples will be given next, but the present invention is not limited thereto.

EXAMPLES In each of the following examples, a set of drawn and ironed tin-plated steel cans (hereinafter DI cans) was contacted with each cleaning solution.

The cans were used within 2 hours of manufacture and were not subjected to any treatment prior to contacting with the cleaning solution of the present invention. A cleaning solution having the component concentrations shown in Table 1 was prepared.

Each composition is identified by a number and subscript "c". Then the specified amount (in ta) of each composition shown in Table D
was added to 6 volumes of water to prepare an alkaline cleaning aqueous solution having the component concentrations shown in Table M. Each wash solution is
” and the composition number used in the formulation. The surfactant was used at the concentration shown in the Table.
The method chosen to contact the cans with the cleaning solution of each example was a spray method. Solutions were sprayed at approximately 25 psi for the times and temperatures indicated in each example. The cans were then rinsed with water and visually observed for etching and appearance. Table 1 Table 0 (Note) ■: 10 indicates that water was used ■: The tap water used was relatively hard with a hardness of about 300 ppm.

Table m Example 1 Apply cleaning solution Is, A, S and an umbrella to a set of DI cans at 1230F (50.6C) for 10 minutes at a rate of one set per solution.
I sprayed it with.

The results are shown in Table W. Table W Example 2 Sets of DI cans were sprayed with cleaning solution $ at a rate of one set per test at the times and temperatures shown in Table V.

The results are shown in Table V. TABLE V EXAMPLE 3 Sets of DI cans were sprayed with cleaning solution $, 7s, $ and $ at the indicated times and temperatures, one set per test.

The results are shown in Table 1. Table 2 Example 4 A set of DI cans was sprayed with 1 melon, 11s and 1 bottle of cleaning solution at a rate of 1 set per test at the indicated time and temperature.

The results are shown on the second skin. Skin table Example 5 An aqueous concentrate having the component concentrations shown in Table 1 was prepared.

These concentrates are designated as 13q and 1 q. 1 dollar and 1 umbrella of alkaline cleaning solution are each made by diluting 11.4 parts of aqueous concentrate (13 q) with tap water to 1 hour, and diluting 10' of aqueous concentrate (1 q) with deionized water in one evening. It was prepared by Surfactants were added at the indicated concentrations. The cleaning solution had the component concentrations shown in the Table of Values. A set of side DI cans, one set per test, was sprayed with 1$ and 1$ of cleaning solution at the indicated times and temperatures.

The results are shown in Table 1. Table X Example 6 Cleaning solutions 1$, 1$ and 17s were prepared using tap water with the component concentrations shown in Table X.

Solution 17s contains no inhibitor and is therefore shown for comparison, as is the cleaning solution core of Example 1. Table
) for the indicated time.

Claims (1)

Claims: 1. having an alkaline component in an amount effective to substantially remove dirt, lubricants or other contaminants from a tin surface, and having quinones, substituted quinones and at least two hydroxy substituents. An aqueous cleaning solution having a pH of 11 to 13 containing an effective amount of an inhibitor selected from the group of substituted benzenes to inhibit etching of the tin surface is applied to the tin surface in an amount effective to substantially remove said contaminants from the tin surface. A method of cleaning a tin surface to substantially remove said contaminants therefrom without visibly etching said surface, characterized in that said surface is contacted at a temperature. 2 Washing temperature 100-130°F (37.8-54.
4°C). 3. The method of item 1 or 2 above, wherein the concentration of the alkaline component in the cleaning liquid is 3 to 5 g/l. 4 The concentration of inhibitor in the cleaning solution is between 0.02 and 0.06 g.
The method of item 3 above, wherein /l. 5 The inhibitor is catechol, resorcinol, hydroquinone, hydroxyhydroquinone, gallic acid, 1,3,5-
The method of item 4 above, selected from the group of trihydroxybenzene, 1,2,4,5-tetrahydroxybenzene, 1,4-benzoquinone, 1,2-benzoquinone, alpha-naphthaquinone and beta-naphthaquinone. 6. Substituted benzenes in which the inhibitor has at least two hydroxy substituents in the ortho, meta, or para positions, symmetrical or asymmetrical arrangement, and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2 , R_3 and R
_4 is hydrogen, hydroxy, alkyl, halo, carboxy, alkoxy, nitro or cyano, or R
_1 and R_2 form an alkyldienyl group, and together with the quinone ring to which they are bonded, they form naphthaquinone. ] The method according to the above item 4, wherein the quinone is selected from the group of quinones and substituted quinones. 7. The method of item 3 above, wherein the alkaline component of the cleaning solution is selected from the group of alkali metal hydroxides, carbonates and silicates, ammonium hydroxides and carbonates, and mixtures thereof. 8. The method of item 7 above, wherein the alkaline component comprises sodium metasilicate, sodium carbonate, and a compound selected from the group of sodium hydroxide and potassium hydroxide. 9. The method of paragraph 1, wherein the cleaning solution comprises an effective amount of polyelectrolyte to substantially prevent precipitation. 10. The method of paragraph 9 above, wherein the amount of polyelectrolyte is at least 0.1 g/l. 11. The method of claim 1, wherein the cleaning solution contains at least 0.2 g/l of one or more surfactants. 12. The method of item 11 above, wherein the concentration of the surfactant is 0.2 to 0.5 g/l. 13. The method of item 11 or 12 above, wherein the cleaning solution contains a low-foaming nonionic surfactant. 14. The method of paragraph 1, wherein the surface is contacted with the cleaning solution by spraying. 15. The method of paragraph 1, comprising rinsing the surface with water after contacting the cleaning solution. 16 an alkaline component in an amount effective to substantially remove dirt, lubricants or other contaminants from the tin surface, and quinones, substituted quinones, and ortho, meta, para, symmetrical or asymmetrical positions; containing an inhibitor selected from the group of substituted benzenes having at least two hydroxy substituents in the sequence;
An aqueous cleaning composition of pH 11-13 for cleaning tin surfaces to substantially remove the contaminants therefrom without visibly etching the surface at a temperature of 54.4°C. 17 Quinones and substituted quinones have formulas ▲ Numerical formulas, chemical formulas, tables, etc. or R_1 and R
_2 forms an alkyldiethyl group, and together with the quinone ring to which they are attached, forms naphthaquinone. ] The cleaning solution of item 16 above. 18. The cleaning solution of item 16 above, wherein the substituent on the benzene ring is hydrogen, halo, alkyl, alkoxy, carboxy, nitro or cyano in addition to the hydroxy substituent. 19 Inhibition control is 1,2-benzoquinone, 1,4-benzoquinone, catechol, resorcinol, 1,4-dihydrobenzoquinone, hydroxyhydroquinone, 1,3,5
-trihydroxybenzene, 1,2,4,5-tetrahydroxybenzene. 20 No. 16 or 1 above, wherein the inhibitor is selected from the group of benzoquinone, 1,4-benzoquinone and substituted quinones.
Cleaning solution in Section 7. 21. The cleaning solution of paragraph 16 above, wherein the inhibitor is selected from the group of dihydroxybenzenes and quinones. 22. The cleaning solution according to paragraph 16 above, wherein the amount of inhibitor is between 0.02 and 0.06 g/l. 23 The alkaline component of the cleaning solution is selected from the group of alkali metal hydroxides, carbonates and silicates, ammonium hydroxides and carbonates, and mixtures thereof.
Cleaning solution in Section 6. 24. The cleaning solution of paragraph 23 above, wherein the alkaline component comprises sodium metasilicate, sodium carbonate, and a mixture of compounds selected from the group of sodium hydroxide and potassium hydroxide. 25. The cleaning solution of paragraph 16 above, containing a polyelectrolyte in an amount effective to substantially prevent precipitation. 26. A cleaning solution according to paragraph 25 above, wherein the amount of polyelectrolyte is at least 0.1 g/l. 27 For cleaning tin surfaces, when added to water at a concentration of 3 to 7 g/l, substantially removes dirt, lubricants or other contaminants from the tin surface without visibly etching it. an alkaline component having a pH of 11 to 13 and an effective amount to substantially remove the above-mentioned contaminants from the tin surface, and quinones, substituted quinones and ortho, meta, para, symmetrical arrangement or asymmetric arrangement. Solid cleaning characterized in that it provides an aqueous alkaline cleaning solution comprising an effective amount of an inhibitor selected from the group of substituted benzenes having at least two hydroxy substituents in a paired arrangement to inhibit etching of a tin surface. Composition for use. 28 Quinones and substituted quinones have formulas ▲ Numerical formulas, chemical formulas, tables, etc. or R_1 and R
_2 forms an alkyldienyl group and, together with the quinone ring to which they are bonded, forms naphthaquinone. ] The solid cleaning composition of item 27 above. 29 In addition to the hydroxy substituent, the substituents on the benzene ring include hydrogen, halo, alkyl, carboxyl, alkoxy,
The solid cleaning composition of item 27 above, which is nitro or cyano. 30 The inhibitor is selected from the group of catechol, resorcinol, hydroquinone, hydroxyhydroquinone, 1,3,5-trihydroxybenzene, 1,2,4,5-tetrahydroxybenzene, 1,4-benzoquinone and 1,2-benzoquinone The solid cleaning composition of item 27 above. 31 The concentration of alkaline component in the composition is at least 15
% by weight of the solid cleaning composition of item 27 above. 32. The solid cleaning composition according to item 27 above, wherein the alkaline component is selected from the group of alkali metal hydroxides, carbonates and silicates, ammonium hydroxides and carbonates, and mixtures thereof. 33 The concentration of inhibitor is at least 0.1% by weight of the composition
The solid cleaning composition of item 27 above. 34. The solid cleaning composition of item 27 above, containing an effective amount of polyelectrolyte to substantially prevent precipitation. 35 When added to water at a concentration of 0.5 to 2% by volume, it cleans tin surfaces substantially removing dirt, lubricants or other contaminants from them without visibly etching them. and an alkaline component in an amount effective to substantially remove the above-mentioned contaminants from the tin surface, and quinones, substituted quinones and ortho, meta, para, symmetrical arrangement or An aqueous concentrate characterized in that it provides an aqueous alkaline cleaning solution containing an effective amount of an inhibitor selected from the group of substituted benzenes having at least two hydroxy substituents in an asymmetric arrangement to inhibit etching of tin surfaces. . 36 Concentration of alkaline component is 770g per liter of concentrated liquid
The concentrated liquid according to item 35 above. 37 The concentration of inhibitor is at least 2 g per liter of concentrate. Concentrated liquid according to item 35 above. 38 The inhibitor is catechol, resorcinol, hydroquinone, hydroxyhydroquinone, 1,3,5-trihydroxybenzene, 1,3,4,
the third selected from the group of 5-tetrahydroxybenzene, 1,4-benzoquinone and 1,2-benzoquinone;
5 or 37 concentrated liquid. 39. The concentrate of paragraph 35 above, containing an effective amount of polyelectrolyte to substantially prevent precipitation. 40 The concentrate of item 35 above, containing one or more surfactants.