JP2012107255A - Alkali detergent for washing aluminum surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali detergent composition which is preferable for washing a metal having corrosion sensitivity in alkali solution, especially for washing a soft metal such as aluminum or its alloy, or a galvanized steel such as a zinc-coated steel, and which can wash the inside surface that is difficult to be reached without additional mechanical treatment.SOLUTION: This invention relates to: a composition for washing a surface having corrosion sensitivity in alkali solution, which contains at least one kind of an alkali source, and at least one kind of an inorganic salt containing at least one kind of cation selected from elements in the second or third main group of the element periodic table, and thereby which does not contain any triazole and/or any alkali metal borate; an aqueous concentrate containing the composition; a solution to be used containing the composition or the aqueous concentrate; and a method for washing the surface having corrosion sensitivity in alkali solution by using the aqueous concentrate or an optional solution to be used.

Description

  The present invention relates to a composition for cleaning a surface that is susceptible to corrosion in an alkaline liquid, an aqueous concentrate comprising the composition, a use solution comprising the composition or the aqueous concentrate, and cleaning such surfaces. On how to do.

  Articles made entirely or partly of various types of metals, and in particular articles having a surface made entirely or partly of metal, play an important role in our daily lives. In general, for example in the house or in the home such as window decorations, furniture, lamps and other household ornaments, for example by sports equipment or with any kind of transportation such as bicycles, motorcycles, boats and cars In our free time of contact, in industrial fields such as manufacturing machines or processing machines, cleaning machines etc., in all forms of transport, in the form of or as part of a constituent material such as a carrier In very specific areas, for example medical devices, and more, we are exposed to such articles many times a day.

  However, since they are generally used with relatively long-life items rather than disposable items, they need to be cleaned from time to time, regardless of where or for what purpose they are used There is. Furthermore, the types of soil that must be removed from the surface of such articles can vary greatly. The soil can also include all kinds of natural or synthetic fats, greases or oils, proteins, pigments and other types of organic and inorganic deposits.

  Unfortunately, many objects, including at least parts made of metal, are susceptible to corrosion, for example, when contacting alkaline liquids for cleaning, and especially when contacting strong alkaline liquids with excellent cleaning properties. is there. Corrosion in alkaline liquids This tendency is particularly true for soft metals such as aluminum, zinc, tin, lead and cadmium, and also for alloys thereof and galvanized steels such as galvanized steel.

  Traditionally, this problem has been avoided by using organic cleaning solvents to clean such surfaces that are sensitive to corrosion in alkaline solutions on the one hand. Typical solvents included hydrocarbon solvents or halogenated hydrocarbon solvents. However, these solvents are usually non-halogenated hydrocarbons that are generally flammable, highly volatile, and uncertain in their ability to be reused for continued use, while halogenated Hydrocarbons are often undesirable because they are often toxic, have a negative impact on the environment, and their waste disposal is relatively expensive.

  Accordingly, many attempts have been made in the past to find materials that can function as corrosion inhibitors but do not adversely affect cleaning performance or the stability of alkaline cleaning compositions. It has been known to use silicates such as alkali metal silicates as corrosion inhibitors since the middle of the 20th century. These compounds are still used because they are relatively effective, especially for surfaces formed from aluminum, aluminum alloys and galvanized steel.

  For example, US Pat. No. 5,862,345 describes a method for removing organic deposits from articles such as those used in the food processing industry. According to this method, a cleaning solution containing at least a peroxygen compound, a metasilicate, a chelate and a builder is applied to the surface. Cleaning with this solution may be allowed to proceed even at low temperatures below 40 ° C.

  However, to use such a silicate composition for cleaning the metal surface described above, the composition remains on the metal surface, for example by insufficient rinsing, and a viscous silicate layer on the metal surface. There is an inconvenience that it causes. Such silicate layers are undesirable for visual and hygienic reasons. However, it is generally very difficult to remove these silicate layers, and it may be necessary to use a highly toxic and difficult-to-work chemical such as a hydrogen fluoride solution. When the above solution is applied on a warm surface that dries the cleaning solution very quickly, or for cleaning surfaces that are difficult to reach and thus are not completely rinsed after the cleaning process, such as, for example, interior surfaces of machines A similar silicate layer may also occur if a cleaning solution is used.

  According to GB541,803, depending on the choice of silicate used and its concentration in the cleaning solution, the surface of aluminum or tin, in particular, may be starred or attacked by the cleaning solution regardless of the presence of the silicate. Is described. According to this document, the above problem is solved by further adding a soluble inorganic mercury salt. However, apart from the disadvantages of using mercury compounds in the cleaning solution, the cleaning solution still contains a silicate that can form a viscous surface layer as described above.

  In order to completely avoid the use of silicate materials, U.S. Pat. No. 5,736,495 describes a metal cleaning comprising a combination of triazole compound and alkali metal borate as an anticorrosive agent in addition to alkali metal salts and surfactants. An agent composition is disclosed. The use of such metal cleaning compositions is exemplified for steel and brass surfaces.

  The latter document includes alkali metal phosphates, borates, molybdates, arsenates, arsenites, nitrates, nitrites, chromates and other inorganic compounds, as well as mercaptobenzothiazoles and benzotriazoles. There are various other known corrosion inhibitors, including various organic compounds such as piperazine, ethylenediaminetetraacetic acid, and the reaction product of phosphoric acid or boric acid with alkanolamines. However, as described in this document, there is still a need to provide further corrosion inhibitors since no inhibitors or combinations of inhibitors for all metals or metal alloys, especially soft metals, have been provided.

  Organic compounds and organometallic compounds have also been used as corrosion inhibitors for quite some time. Pyridine, diethylthiourea, toluidine derivatives or mixtures thereof are examples of such corrosion inhibitors commonly employed. In addition, tributyltin and tributyltin naphthanate have been used in marine paints and barium, calcium or magnesium sulfonates, phenolates and salicylates have been added to the oil additives. However, such compounds are no longer desirable due to environmental reasons and their toxicity.

  In addition, when developing compositions for cleaning the metal surfaces described above, the outer surface, which is typically more easily accessible, must be considered, and the inner surface is often difficult to reach. There is also a need for cleaning. In particular, if the inner surface is involved, cleaning must be done without the need for additional mechanical treatment of the surface.

  Therefore, the problem inherent in the present invention is that for cleaning metals that are susceptible to corrosion in alkaline solutions, particularly for cleaning soft metals such as aluminum or its alloys, or galvanized steels such as galvanized steel. The object is to provide an alkaline cleaning composition which is suitable for and which allows the cleaning of inner surfaces which are difficult to reach without the need for additional mechanical treatment.

  The above-described problem is a composition for cleaning a surface that is susceptible to corrosion in an alkaline solution, and is selected from at least one alkali source and an element of the second or third main group of the periodic table. By including at least one inorganic salt comprising at least one cation, the composition is solved by a composition that does not contain any triazole and / or any alkali metal borate.

  The above composition is applied to the surface to be cleaned, preferably in the form of its aqueous solution. While aqueous solutions of the above compositions can also be applied over surfaces formed with other metals, the cleaning composition of the present invention can be applied to aluminum, zinc, tin, lead, cadmium, alloys thereof, Or, it is particularly preferred for use in cleaning surfaces formed of soft metals such as those plated with any of these metals such as galvanized steel. More preferably, the composition is used to clean surfaces formed of aluminum, aluminum alloys or galvanized steel.

The at least one inorganic salt includes at least one cation selected from the elements of the second or third main group of the periodic table. The corresponding element should at least partially have metallic properties. This means that while aluminum cations and germanium ions are preferred cations in the present invention, the use of compounds containing boron cations is not preferred. Gallium, indium and thallium cations can also generally be used in the salts according to the invention, but the cations are from Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Al ³⁺ or mixtures thereof. Is preferably selected from the group consisting of Ca ²⁺ is indicated as the most preferred cation.

In a preferred embodiment, the anion forming the counterion of the cation in the salt according to the invention is selected from the group comprising halides, in particular chloride, bromide or iodide, sulfate and carbonate. It is also possible to use double salts, ie salts formed with two or more different salts that have a single stoichiometric ratio and crystallize simultaneously. The corresponding anions in such double salts can be the same as in CaMg (CO ₃ ) ₂ or different as in apatite (Ca ₅ (PO ₄ ) ₃ F). However, it is preferable not to use double salts.

Oxides of the above-mentioned elements of the second or third main group of the periodic table can also be included in the composition of the present invention, especially oxides such as MgO, CaO or Al ₂ O ₃ Not included in this.

Common suitable salts for the composition according to the invention are not limited to readily soluble salts. The use of sparingly soluble salts such as calcium carbonate, magnesium carbonate or calcium sulfate is also possible.
Nevertheless, salts that are readily soluble and have reduced risk of precipitation during the washing process are preferred in the composition according to the present invention.

  In particularly advantageous embodiments, the one or more salts are present in the composition in a total amount based on the total composition of 0.01 to 20 wt%, preferably 0.05 to 15 wt%, and more preferably Is contained in an amount of 0.1 to 3.5 wt%.

  Suitable alkali sources for use in the compositions of the present invention are alkali metal salts that can typically be rendered alkaline in an aqueous solution that removes dirt deposited on the metal surface. Depending on the adoption of the article comprising at least one surface or part thereof that is to be cleaned, various types of soils may be deposited thereon. Examples of such soils include any type of natural or synthetic fats, greases, waxes or oils, proteins, carbohydrates, burned carbon, and carbonized such as those formed in food processing machines or households. Examples include organic matter, pigments and pigments, minerals, human and animal waste and other types of organic and even inorganic deposits and mixtures thereof. The alkalinity of the composition according to the present invention should be sufficiently high so that the aqueous solution can remove the main part of each stain.

  Suitable alkali sources for the compositions of the present invention include sodium hydroxide, potassium hydroxide, potassium and sodium carbonate and their hydrates, sodium and potassium bicarbonate, trisodium orthophosphate, ortholine Tripotassium, sodium or potassium pyrophosphate, tripolyphosphate and hexametaphosphate, alkali metal acetate, citrate, tartrate, succinate, phosphonate, calcium hydroxide or barium hydroxide, etc. Examples include alkali metal orthophosphates or complex phosphates such as alkaline earth hydroxides, or mixtures thereof. However, it is preferred to use sodium hydroxide, potassium hydroxide or mixtures thereof. Preferably, these compounds are used in their solid form.

  In most cases, particularly when sodium or potassium hydroxide functions as the alkali source, the alkali source is present in the composition in a total amount of 1 to 40 wt%, preferably 2 to 30 wt%, based on the total composition, And more preferably 5 to 25 wt% will suffice.

  In order to obtain acceptable or even better cleaning performance, the aqueous solution obtained from the composition has a pH value (1%, 20 ° C., demineralized water) of 9 to 13, preferably 10 to 12, more preferably more than 11. There should be.

  Cleaning metal surfaces, particularly aluminum, aluminum alloys or galvanized steels with aqueous solutions exhibiting high pH values obtained from such compositions typically results in corrosive action and ultimately decomposition of the metal surface. Brought about. Surprisingly, however, such corrosive action and metal surfaces in the presence of the above-mentioned salts comprising one or more cations selected from the elements of the second or third main group of the periodic table It was found that no degradation of was observed. Therefore, it can be inferred that these inorganic salts function as corrosion inhibitors for the aforementioned metal surface in the aqueous alkaline composition.

  Furthermore, it is surprisingly surprising that when the aforementioned inorganic salts are used in an aqueous solution of the composition according to the invention, the use of alkali metal silicates or any other compounds based on silicon is no longer necessary. Therefore, the composition according to the present invention preferably does not contain any compound or elemental silicon containing silicon.

  Furthermore, in the presence of the inorganic salt described above, one or more organometallic compounds are used as corrosion inhibitors in an alkaline solution for the purpose of cleaning a metal surface that is susceptible to corrosion under such conditions. It is also unnecessary to use. As a result, in a preferred embodiment, the composition according to the present invention does not contain any organometallic compound. Here, “organometallic compound” is intended to mean an elemental organic compound having a direct metal-carbon bond. Metal salts of organic acids, alcoholates, crown compounds and other inclusion compounds, and chelates and metal acetylacetonates are not considered organometallic compounds, while silicones, organophosphate compounds, organoarsenic compounds and organoboron compounds Denotes an organometallic compound in the sense of the present invention.

  The compositions of the present invention are also typically in alkaline cleaning compositions, such as sequestering agents, surfactants, bactericides, bleaches, oxidizing agents, builders, solubilizers, solvents or mixtures thereof. Contains other ingredients used. Some of these compounds also have various functions. For example, oxidizing agents such as hypochlorite that produce active chlorine also exhibit bactericidal properties in addition to these cleaning promoting properties. In such cases, the total amount of a particular substance that can be included in the composition according to the present invention can represent the sum obtained from the addition of the amounts of a single component corresponding to its various properties. For example, if the amount of oxidizer in the composition is intended to not exceed 40 wt% based on the total composition, then if a bactericidal agent may be present in addition to the oxidizer, Regardless of this, the amount of chlorite exceeds 40 wt%.

  The composition according to the present invention preferably contains one or more oxidizing agents. Suitable oxidizing agents are one or more that produce active chlorine such as hypochlorous acid, exemplified by lime chloride, calcium hypochlorite, sodium hypochlorite and potassium hypochlorite. It can be expressed as a compound. However, peroxygen compounds such as perborate or percarbonate, preferably with a metal such as sodium, lithium, calcium or potassium, or hydrogen peroxide may be more suitable as an oxidizing agent. Preferably, however, the compositions of the present invention do not contain any alkali metal perborate. In particularly preferred embodiments, the compositions of the present invention comprise sodium hypochlorite, potassium hypochlorite or mixtures thereof and are free of other bleaching or oxidizing agents.

  One or more oxidizing agents are present in the composition according to the invention in a total amount based on the whole composition of 30 to 80 wt%, preferably 35 to 70 wt%, and more preferably 40 to 65 wt%. Good to be included.

  Surprisingly, the cations used in the aqueous solution of the composition according to the invention do not cause any degradation of hypochlorite which may also be present in the composition. However, the stability of the aqueous solution formed with the composition and the stability of the salt in the alkaline solution can be improved by further adding one or more sequestering agents to the composition. . This is especially true for calcium and magnesium as cations, which are due to the formation of water insoluble hydroxides in alkaline solutions. Suitable sequestering agents include: ethylenediaminetetraacetic acid, nitrilotriacetic acid, phosphates, especially polyphosphates such as pentasodium triphosphate, polyhydroxycarboxylic acids, citrates, especially alkali citrates, dimercaprol , Triethanolamine, crown compound or phosphonoalkane polycarboxylic acid. In an aqueous solution under alkaline conditions, the aforementioned acids may usually be present in the form of their salts, preferably in the form of their sodium or potassium salts. However, when producing the composition according to the invention, the acid can be used in the same manner as the corresponding salt.

  The phosphonoalkane polycarboxylic acid preferably comprises a linear hydrocarbon backbone having 3 to 6 carbon atoms and 2 to 5 carboxylic acid moieties. A particularly preferred phosphonoalkane polycarboxylic acid is 2-phosphonobutane-1,2,4-3 acetic acid. These compounds are particularly advantageous in combination with calcium or magnesium containing corrosion inhibitor salts.

  One or more sequestering agents are used in the composition in a total amount of 2 to 35 wt%, preferably 5 to 25 wt%, based on the entire composition, in order to obtain sufficient sequestration performance. And more preferably 9 to 20 wt%.

  In some cases, improved cleaning performance of an aqueous solution formed from the composition according to the present invention can be realized when one or more surfactants are further added to the composition. However, when surfactants are used, it must be ensured that they are functioning under the strong alkaline conditions of the solution obtained from the composition. Although all types of anionic, cationic, nonionic and amphoteric surfactants can be applied, particularly suitable surfactants for use in the present invention include anionic and / or nonionic interfaces An active agent is indicated.

  Suitable anionic surfactants include alkyl arene sulfonates, especially alkyl benzene sulfonates and alkyl naphthalene sulfonates, alkyl sulfonates, preferably those containing 12 to 18 carbon atoms in the alkyl moiety, α-olefin sulfonates, preferably 12 Examples include those containing from 1 to 17 carbon atoms in the olefin moiety, or alkyl sulfates, preferably those having from 11 to 17 carbon atoms in the alkyl moiety, or mixtures thereof. Usually, the above compounds are used in the form of their alkali salts, in particular in the form of their sodium salts. A particularly advantageous anionic surfactant is sodium lauryl sulfate. An anionic surfactant can improve the cleaning performance and the stability of the composition.

  Other known nonionic surfactants such as alkoxylated, in particular ethoxylated and / or propoxylated fatty alcohols or amines, which may also be alkyl-terminated, for example butyl-terminated, Is preferred in the composition according to the invention, but the formula

Wherein R ¹ to R ³ independently represent an aliphatic or cyclic hydrocarbon residue having 1 to 20 carbon atoms, wherein at least one of R ¹ to R ³ and preferably 1 It is more preferred to use an amine oxide corresponding to a hydrocarbon residue having 11 or more carbon atoms. It is also possible to use a mixture of several amine oxides. Preferable amine oxides are coconut alkyl dimethylamine oxide or lauryl dimethylamine oxide.

  Additional nonionic surfactants that can be used in the compositions of the present invention include alkyl polyglucosides. The alkyl group of the alkyl polyglucoside is generally derived from natural fats or oils or petrochemically produced alcohols. The sugar moiety is typically derived from a reducing sugar having 5 to 6 carbon atoms.

  Examples of the cationic surfactant used in the composition according to the present invention include quaternary ammonium salts. These preferably indicate saturated or unsaturated compounds derived from the esterification of trialkanolamines, in particular triethanolamine, with fatty acids and subsequently quaternization with suitable alkylating reagents. Suitable fatty acids are lauric acid, myristic acid, palmitic acid, oleic acid or stearic acid having 12 to 18 carbon atoms. In particular, it is preferred to use a mixture of fatty acids obtained in a technical process such as an acid mixture derived from coconut oil, palm kernel oil, rapeseed oil or tallow oil.

  In particularly preferred embodiments, the one or more surfactants are present in the composition in a total amount of 1 to 30 wt%, preferably 2 to 20 wt%, and more preferably 4 to 15 wt% based on the total composition. %included.

  Depending on the type of soil and the form and location of the metal surface to be cleaned, in view of the above description, foamed or non-foamed detergents (where non-foamed are all types of surfactants) Either by omitting the agent completely or by using a low foaming surfactant).

  It may be useful to further add one or more solubilizers to obtain a uniform solution from the above composition. In particular, these facilitate the dispersion of an organic component such as one or more surfactants in an aqueous solution. Suitable solubilizers include xylene, toluene, ethyl benzoate, isopropyl benzene, naphthalene or alkyl naphthalenes sulfonates such as sodium, potassium, ammonium and alkanol ammonium salts, alkoxylated alkylphenol phosphates, alkoxylated alcohol phosphorus Examples include acid esters, and sodium, potassium and ammonium salts of alkyl sarcosinates, and mixtures thereof.

  In a preferred embodiment, one or more solubilizers are included in the composition in a total amount of 1 to 35 wt%, preferably 5 to 25 wt%, and more preferably 9 to 20 wt%.

  The composition according to the present invention further comprises one or more other compounds commonly used in cleaning compositions, such as those selected from the group comprising fungicides, builder substances, solvents and bleaches. May be included. Such compounds are preferably included in the composition according to the invention in a total amount of 0 to 20 wt%, preferably 2 to 15 wt%, more preferably less than 10 wt%.

  Typically, the compounds exemplified above with respect to the oxidizing agent also function as a bleaching agent. However, this does not exclude the use of compounds not mentioned above as bleaching agents.

  Suitable builders include sodium carbonate, sodium sesquicarbonate, sodium sulfate, sodium bicarbonate, phosphate such as trisodium phosphate, nitrilotriacetic acid or each of its salts, citric acid or each of its salts, The mixture of is illustrated.

  Also suitable disinfectants are those described above with respect to oxidizing agents for use in the compositions according to the invention, and aldehydes such as formaldehyde, glyoxal or glutaraldehyde, phenol derivatives and alcohols or mixtures thereof are indicated.

  In a preferred embodiment, the composition according to the invention is present in the form of a powder or solid block. The production of the washing powder or solid block proceeds according to the procedure described in the description of the technology. For example, the powder can be obtained by preparing an aqueous slurry of the above composition and spraying under high pressure through a nozzle at the top of the drying tower to form a hollow sphere powder.

  The composition can be formed into a solid block by first melting the alkali source, preferably located in the cartridge, and adding the other components of the composition to the melt. Other components are first anionic and nonionic surfactants, then single or multiple sequestering agents, single or multiple oxidizing agents, single or multiple solubilization After continuously adding the agent, it is preferred to maintain the component until the component is incorporated.

  As described above, the composition according to the present invention is applied to the solution to be cleaned in the form of an aqueous solution. The aqueous solution can be formed directly before use or can be formed beforehand. If the solution is formed directly prior to use, preferably the composition in the form of a powder or solid block as described above is dispersed in the desired amount and then dissolved in the desired amount of water to obtain a predetermined concentration of use solution. it can. However, when the composition is used in the form of a solid block, it is also possible to obtain a use solution by rinsing the solid block with a predetermined amount of water to obtain a use solution having a predetermined concentration.

  In addition, the aqueous cleaning solution can be stored after it is formed, rather than directly before use, until needed. Accordingly, a further subject of the present invention is an aqueous concentrate comprising the above-described composition and free water. Here, free water means pure water. One or more compounds are not used in solid form, but when used in the form of these aqueous solutions, additional water is included in addition to pure water added to dissolve a single component of the composition. It may be. For example, the alkali source or the surfactant may be dissolved in water when the aqueous solution according to the present invention is produced. However, if the composition is present in the form of a powder or solid block, preferably no single component is used in the form of these aqueous solutions, whereas for preparing the aqueous solutions according to the invention these components are not used. The use of the compound as an aqueous solution facilitates the production of an aqueous wash concentrate.

  Preferably, the water is desalted and is included in the concentrate in an amount of 30 to 90 wt%, more preferably 35 to 88 wt%, and most preferably 40 to 85 wt%.

  The aforementioned aqueous concentrate preferably comprises the cleaning composition described above in an amount of 30 to 95 wt%, preferably 35 to 90 wt%, and more preferably 40 to 85 wt%, based on the entire aqueous concentrate.

  Further, the aqueous concentrate according to the present invention comprises one or more salts in a total amount based on the whole concentrate of 0.01 to 10 wt%, preferably 0.05 to 5 wt%, and more preferably Contains 0.1 to 3.5 wt%.

  In a preferred embodiment, the alkali source is included in the aqueous concentrate in a total amount of 1.5 to 20 wt%, preferably 2 to 10 wt%, and more preferably 3 to 5 wt% based on the entire concentrate. It is particularly preferred that the concentrate has a pH value (1%, 20 ° C.) of 9 to 13, preferably 10 to 12, more preferably more than 11.

  In addition, one or more sequestering agents may be present in the aqueous concentrate in a total amount of 1 to 10 wt%, preferably 2 to 8 wt%, and more preferably 3 to 5 wt% based on the entire concentrate. included.

  The aqueous concentrate according to the invention is preferably 1 to 15 wt%, preferably 2 to 10 wt%, and more preferably 2 with one or more surfactants, based on the total concentrate. 3 to 6 wt%.

  In addition, one or more oxidizing agents are included in the concentrate in a total amount of 10 to 40 wt%, preferably 15 to 30 wt%, and more preferably 20 to 28 wt% based on the entire concentrate. Since percarbonate and perborate are not stable in alkaline solution, the aqueous concentrate preferably does not contain any of these compounds.

  Aqueous concentrates are monohydric or polyhydric alcohols or glycol ethers, in particular ethanol, n-propanol or i-propanol, butanol, glycol, propanediol, butanediol, glycerol, diglycol, propyldiglycol, butyldiglycol. Glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or propylene glycol mono Propyl ether, dipropylene glycol monomethyl ether, di Selected from propylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol mono-tert-butyl ether and mixtures thereof One or more kinds of solvents may be further included.

  In order to obtain optimal cleaning results, the aqueous cleaning concentrate according to the invention should be a homogeneous solution. Therefore, the concentrate according to the present invention is preferably produced by first dissolving the corrosion inhibitor salt in water and then adding other components thereto. The order of addition is not particularly limited. First, one or more alkali sources are added, and then an anionic surfactant, a nonionic surfactant, a sequestering agent, an oxidizing agent, and a solubilizing agent. It is advantageous to add and then maintain the ingredients until they are incorporated. It is also possible not to dissolve the corrosion inhibitor salt first but to add it at the end of the production of the concentrate. If the corrosion inhibitor salt is sparingly soluble, it can first be dissolved, for example, in an acid, neutralized, and then mixed with other ingredients.

  The aforementioned aqueous concentrate can be used for cleaning the metal surface as described above, etc., or preferably further diluted with water or any of the aforementioned solvents or mixtures thereof. In a preferred embodiment, the concentrate is diluted with water so that the concentrate according to the invention is 0.1 to 10 wt%, preferably 0.5 to 8 wt%, more preferably 1 to 0% based on the total use solution. An aqueous working solution containing 5 wt% is obtained.

  Accordingly, a further subject of the present invention is an aqueous concentrate according to the invention for cleaning surfaces that are sensitive to corrosion in alkaline liquids, based on the total working solution, preferably 0.1 to 10 wt%, preferably 0 An aqueous use solution containing 5 to 8 wt%, more preferably 1 to 5 wt%.

  As mentioned above, the use solution can also be obtained directly from the cleaning composition itself or in the form of a powder or solid block. Accordingly, a further object of the present invention is an aqueous use solution for cleaning surfaces that are susceptible to corrosion in alkaline liquids, wherein the composition as defined above, in powder or solid block form, is used as a whole. It relates to those containing 0.05 to 8 wt%, preferably 0.1 to 5 wt%, more preferably 0.3 to 3 wt%.

  Another subject of the invention is a method for cleaning a surface which is sensitive to corrosion in an alkaline liquid, using the aforementioned aqueous concentrate according to the invention or any of the aforementioned use solutions.

  The use of aqueous cleaning concentrates or use solutions is not limited to those that are corrosion sensitive in alkaline liquids, but, as with the aqueous cleaning concentrates or use solutions that do not cause corrosion of the present invention, Its use on metal surfaces is one major advantage. In particular, the aqueous cleaning concentrates or use solutions according to the invention are made of aluminum, tin, zinc, lead or cadmium, their alloys, or other metals or galvanized steels, in particular steels plated with any of these metals. Suitable for application to clean soft metal surfaces such as alloys. The most preferred metal surface is formed of aluminum, aluminum alloy or galvanized steel. The main alloy additions for aluminum alloys are preferably copper, magnesium, silicon, manganese and zinc.

  In a preferred embodiment according to the method of the present invention, the surface to be cleaned is first contacted with the aqueous cleaning concentrate or use solution according to the present invention. Thereafter, the contacted surface is optionally rinsed and / or dried. Contact of the aqueous cleaning concentrate or use solution with the metal surface may immerse the metal surface in the aqueous cleaning concentrate or use solution or provide the aqueous cleaning concentrate or use solution on the surface, for example by spraying or pouring. Etc., and can be obtained by a general method known in the art.

The contact time for obtaining sufficient cleaning results can range from a few seconds to several hours.
Preferably, it is in the range of 30 seconds to 2 hours, more preferably 1 minute to 30 minutes. The contact time gives one contact for the entire contact time, or the aqueous cleaning of the metal surface for a time corresponding to the sum of each shorter contact time at a given shorter time This can be achieved by continuously contacting the concentrate or the solution used.

  Cleaning results can be improved by vigorously stirring the aqueous cleaning concentrate or use solution throughout the entire contact time or for a predetermined portion of the total contact time. It may be useful to raise the temperature of the aqueous wash concentrate or use solution to, for example, 20 to 90 ° C, preferably 40 to 60 ° C.

  The method of the present invention relates to the cleaning of an outer surface, e.g., the inner surface of the article, or both the outer and inner surfaces of the article. In connection with the difficulty of reaching the corresponding surface, the cleaning method for the outer surface is likely to be different from the cleaning method for the inner surface. Typically, to clean the outer surface, the article remains intact and the cleaning solution is applied over the surface that is to be cleaned. For example, when cleaning an inner surface of an article or machine, it may be necessary to disassemble the relevant part of the article or machine, including the surface that is to be cleaned, because the cleaning solution or the like may not reach the surface It may be. This procedure is often referred to as decomposition cleaning (COP). Such a procedure is preferably performed at ambient temperature (typically room temperature). However, it may be appropriate to raise the temperature to 60 ° C.

  However, a further method of cleaning the inner surface of an article or machine that is difficult to reach is through the article or machine under conditions where the surface that is to be cleaned by circulation is in contact with an aqueous cleaning concentrate or use solution. There are methods of circulating an aqueous wash concentrate or use solution. This procedure is often referred to as in-place cleaning (CIP). Such a procedure is preferably carried out in the aforementioned temperature range. Both methods of cleaning (COP and CIP) are possible when using an aqueous cleaning concentrate or use solution according to the invention.

  The cleaning method according to the present invention can proceed manually or automatically. If washing proceeds automatically, the process can be fully or partially automatic.

  The method according to the invention can be applied for cleaning purposes for facilities and homes.

  Examples of surfaces that can be cleaned by the method according to the present invention include window frames, exterior surfaces, dishwashers, and certain metals such as wash dryers or passenger wash dryers that include a sidewalk behind the wash dryer Manufacture and packaging of machines, beauty care compounds, pharmaceuticals or civilian goods such as (automatic) washing machines, packaging machines, manufacturing machines or processing machines in all types of industrial fields such as food and beverage processing machines Machinery, medical equipment and equipment, tanks, pipe devices, filling machines, pots, (fry) pans, ornaments, furniture or parts thereof, frames and all kinds of cars, trucks, ships, boats Shown are metal surfaces that can be found in the home, such as vehicle-related surfaces such as bicycles or motorcycles.

  The invention is further illustrated by the following examples. All amounts are expressed in wt% unless otherwise specified.

Examples Table 1 shows examples of aqueous concentrates (No. 1 to 20) according to the present invention and comparative examples (21 to 26) which do not contain any corrosion inhibitor salt according to the present invention. All compositions were obtained by first dissolving the corrosion inhibitor salt in a predetermined amount of water and adding the remaining contents in the order listed in the table. The mixture was stirred until a homogeneous solution was obtained.

  In Table 1, Examples 1 to 7 and Comparative Example 1 represent alkaline foam cleaners that also provide active chlorine. Such cleaning agents can also be used for manual cleaning. The active chlorine in the cleaning agent exhibits bactericidal properties in addition to cleaning promoting properties.

  Examples 8 to 10 and Comparative Example 2 represent alkali non-foaming detergents that also provide active chlorine. It is possible to add further non-foaming surfactants that are resistant to active chlorine. The active chlorine in the cleaning agent exhibits bactericidal properties in addition to cleaning promoting properties.

  Examples 11-13 and Comparative Example 3 represent alkaline foam cleaners that do not provide active chlorine. Such cleaning agents can also be used for manual cleaning.

  Examples 14 to 16 and Comparative Example 4 represent non-foaming detergents that do not provide active chlorine. It is also possible to add further non-foaming surfactants.

  Examples 17-20 and Comparative Examples 5 and 6 represent alkaline foam cleaners that provide active chlorine of a different type than the selected corrosion inhibitor salt. These cleaning agents can also be used for manual cleaning.

  Table 2 shows the substance affinity results using the compositions according to Table 1. Only the compositions according to Comparative Examples 5 and 6 could not be tested because they were not stable. The affinity test was performed at a temperature of 20 ° C. Aluminum and galvanized (Zn) steel test plates, each 5 × 10 cm in size, were weighed and then completely immersed in an aqueous solution containing 5% single composition for 1 hour. After this time, the test plate was removed from the solution and weighed again to assess mass loss. For comparison purposes, Comparative Example 1 is repeated when showing the results of Examples 17-20.

From the data shown in Table 2, it is clear that the mass loss due to the corrosive action resulting from the cleaning composition decreases with increasing amount of the corrosion inhibitor salt according to the present application. The best results have been obtained using CaCl ₂ as a corrosion inhibitor salt.

  The cleaning properties were tested with several selected compositions. The cleaning properties were evaluated using 5 × 10 cm size aluminum (99.8) plates each stained with 1 g of tallow. The test plate was immersed 10 times per minute in a cleaning solution containing 2 wt% of the corresponding composition in demineralized water. The test was conducted at a solution temperature of 38 ° C. The results are shown in Table 3.

The data in Table 3 shows that the cleaning composition according to the present invention in most cases exhibits very good cleaning properties on an aluminum plate compared to a solution consisting only of water.
[1]
A composition for cleaning a surface that is susceptible to corrosion in an alkaline liquid, comprising at least one alkali source and at least one element selected from elements of the second or third main group of the periodic table A composition wherein the composition does not comprise any triazole and / or any alkali metal borate by comprising at least one inorganic salt comprising a cation.
[2]
The composition according to [1], wherein the cation is selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Al ³⁺ or a mixture thereof.
[3]
The composition according to [1] or [2], characterized in that the anion counterion to the cation is selected from the group comprising halides, in particular chloride, bromide or iodide, sulfate and carbonate.
[4]
One or more salts are present in the composition in a total amount of 0.01 to 20 wt%, preferably 0.05 to 15 wt%, and more preferably 0.1 to 10 wt%, based on the total composition. It is contained, The composition in any one of [1]-[3] characterized by the above-mentioned.
[5]
The alkali source is contained in the composition in a total amount of 1 to 40 wt%, preferably 2 to 30 wt%, and more preferably 5 to 25 wt% based on the total composition [1] To [4].
[6]
The composition according to any one of [1] to [5], which does not contain any compound containing silicon.
[7]
The composition according to any one of [1] to [6], which does not contain any organometallic compound.
[8]
The composition according to any one of [1] to [7], further comprising one or more sequestering agents.
[9]
The one or more sequestering agents are included in the composition in a total amount of 2 to 35 wt%, preferably 5 to 25 wt%, and more preferably 9 to 20 wt% based on the total composition. The composition according to [8], wherein
[10]
The composition according to [8] or [9], wherein the sequestering agent is phosphonoalkanepolycarboxylic acid or a salt thereof, preferably a sodium salt or a potassium salt thereof.
[11]
The composition according to any one of [1] to [10], wherein the composition further comprises one or more surfactants.
[12]
[1] The composition according to [11], wherein the one or more surfactants are selected from an anionic surfactant and / or a nonionic surfactant.
[13]
The one or more surfactants are contained in the composition in a total amount of 1 to 30 wt%, preferably 2 to 20 wt%, and more preferably 4 to 15 wt% based on the entire composition. The composition according to [11] or [12], wherein
[14]
The composition according to any one of [1] to [13], further comprising one or more oxidizing agents.
[15]
The composition according to [14], wherein the oxidizing agent contains one or more chlorine sources.
[16]
The one or more oxidizing agents are included in the composition in a total amount of 30 to 80 wt%, preferably 35 to 70 wt%, and more preferably 40 to 65 wt% based on the total composition. The composition according to [14] or [15], which is characterized.
[17]
The composition according to any one of [1] to [16], further comprising one or more solubilizers.
[18]
The one or more solubilizers are included in the composition in a total amount of 1 to 35 wt%, preferably 5 to 25 wt%, and more preferably 9 to 20 wt% based on the total composition. [17] The composition according to [17].
[19]
Any one of [1] to [18], wherein the composition further comprises one or more compounds selected from the group comprising a bactericide, a builder substance, a solvent and a bleaching agent. The composition as described.
[20]
The composition according to any one of [1] to [19], wherein the composition exists in the form of a powder or a solid block.
[21]
An aqueous concentrate comprising the composition according to any one of [1] to [19] and free water.
[22]
The aqueous concentrate according to [21], characterized in that it comprises the composition in an amount of 30 to 95 wt%, preferably 35 to 90 wt%, and more preferably 40 to 85 wt%, based on the entire aqueous concentrate. object.
[23]
[21] or characterized in that water is present in the composition in an amount of 30 to 90 wt%, preferably 35 to 88 wt%, more preferably 40 to 85 wt%, based on the total aqueous concentrate. [22] The aqueous concentrate according to [22].
[24]
One or more salts are in the concentrate in a total amount based on the total concentrate of 0.01 to 10 wt%, preferably 0.05 to 5 wt%, and more preferably 0.1 to 3. 5 wt% is contained, The aqueous concentrate in any one of [21]-[23] characterized by the above-mentioned.
[25]
The alkali source is contained in the concentrate in a total amount of 1.5 to 20 wt%, preferably 2 to 10 wt%, and more preferably 3 to 5 wt% based on the entire concentrate [21 ] The aqueous concentrate in any one of [24].
[26]
[21] to [25], characterized in that the concentrate has a pH value (1%, 20 ° C) in the range of 9 to 13, preferably in the range of 10 to 12, more preferably more than 11. ] The aqueous concentrate in any one of.
[27]
One or more sequestering agents are included in the concentrate in a total amount of 1 to 10 wt%, preferably 2 to 8 wt%, and more preferably 3 to 5 wt% based on the entire concentrate The aqueous concentrate according to any one of [21] to [26].
[28]
One or more surfactants are included in the concentrate in a total amount of 1 to 15 wt%, preferably 2 to 10 wt%, and more preferably 2.3 to 6 wt% based on the entire concentrate The aqueous concentrate according to any one of [21] to [27], wherein
[29]
One or more oxidizing agents are contained in the concentrate in a total amount of 10 to 40 wt%, preferably 15 to 30 wt%, and more preferably 20 to 28 wt% based on the entire concentrate The aqueous concentrate according to any one of [21] to [28].
[30]
An aqueous use solution for cleaning a surface that is susceptible to corrosion in an alkaline solution, the composition according to any one of [1] to [20], from 0.05 to An aqueous use solution comprising 8 wt%, preferably 0.1 to 5 wt%, more preferably 0.3 to 3 wt%.
[31]
An aqueous use solution for cleaning a surface that is susceptible to corrosion in an alkaline solution, wherein the aqueous concentrate according to any one of [21] to [29] is 0.1% based on the entire use solution. From 10 to 10 wt%, preferably 0.5 to 8 wt%, more preferably 1 to 5 wt%.
[32]
A method for cleaning a corrosion-sensitive surface in an alkaline liquid using the aqueous concentrate according to any one of [21] to [29] or the use solution according to [30] or [31].
[33]
[32] The method according to [32], wherein the cleaning surface is formed of a material selected from the group including aluminum, aluminum alloys, and galvanized steel.
[34]
[32] or [33], characterized in that the surface to be cleaned is optionally rinsed and / or dried after contact with an aqueous concentrate or any use solution the method of.
[35]
The method according to any one of [32] to [34], which is used for cleaning an outer surface formed of a metal and / or an inner surface formed of a metal.
[36]
The method according to any one of [32] to [35], wherein the method is used for stationary cleaning (CIP) or decomposition cleaning (COP).
[37]
[37] The method according to any one of [32] to [36], wherein the cleaning is performed manually or automatically, and the automatic cleaning can be completely or partially automatic.
[38]
The method according to any one of [32] to [37], wherein the aqueous concentrate or any use solution is used for cleaning in facilities and / or households.

Claims (9)

An aqueous wash solution comprising a composition for cleaning a surface that is corrosion sensitive in alkaline solution, said composition, at least one source of alkalinity, and ^{Mg 2+, Ca 2+, Sr 2+} , Including at least one cation selected from the group consisting of Ba ²⁺ , Al ^3+, or a mixture thereof, and an anion counterion to the cation selected from the group including halide and sulfate Comprising at least one inorganic salt, the composition further comprising an anionic surfactant or an amine oxide, wherein the composition comprises 2 to 35 wt% phosphonoalkane polycarboxylic acid or salt thereof as a sequestering agent. Further comprising, the aqueous cleaning solution wherein the composition does not contain any triazole and / or any alkali metal borate. The aqueous cleaning solution according to claim 1, wherein one or more salts are contained in the composition in a total amount of 0.01 to 20 wt% based on the entire composition. The aqueous cleaning solution according to claim 1 or 2, wherein the alkali source is contained in the composition in a total amount of 1 to 40 wt% based on the whole composition. The composition, characterized in that it does not contain any compound containing silicon, aqueous cleaning solution according to any one of claims 1 to 3. The composition, characterized in that it does not contain any organometallic compounds, aqueous cleaning solution according to any one of claims 1 to 4. Characterized in that the anionic surfactant is sodium lauryl sulfate, the aqueous cleaning solution according to any one of claims 1 to 5. Characterized in that said amine oxide is a coconut alkyl dimethyl amine oxide or lauryl dimethyl amine oxide, the aqueous cleaning solution according to any one of claims 1 to 5. 8. Aqueous cleaning solution according to any one of the preceding claims, characterized in that it is an aqueous concentrate containing the composition in an amount of 30 to 95 wt%, based on the entire aqueous concentrate. Aqueous cleaning solution according to any one of the preceding claims, characterized in that it is an aqueous use solution containing the composition in an amount of 0.05 to 8 wt% based on the total aqueous use solution. .