Degreasing solution and degreasing method

Abstract: Using a degreasing solution not containing a phosphorus compound which may badly affect environment, degreasing treatment showing a low foaming character as well as an excellent degreasing character is applied for a matter to be processed consisting of one kind or more of metal materials among iron, zinc, aluminum, and alloys containing two kinds or more of these metals, and thereby, the matter to be processed is converted into such as having an excellent conversion coating performance. A method for degreasing a matter to be processed by bringing a degreasing solution in contact with said matter to be processed, wherein said degreasing solution contains an alkali silicate, a water-soluble polycarboxylate and a nonionic surfactant and satisfies the following 1 ○, 2 ○, 3 ○ and 4 ○ conditions. 1 ○ The pH value of the degreasing solution is 10.5 or more. 2 ○ The concentration of an alkali silicate is 100 ppm or more upon converting into the Si element and satisfactory for the following ( a ) equation. log ₁₀ Y ≦ 0.318 X + 2.72 (a) [ in the equation, Y denotes the concentration of an alkali silicate ( upon converting into Si and by a ppm unit ), X = pH - 10.5, and this pH denotes the pH value of the degreasing solution. ] 3 ○ The concentration of a water-soluble polycarboxylate is in a range of from 0.01 to 10 g/liter. 4 ○ The concentration of a nonionic surfactant is in a range of from 0.01 to 10 g/liter.

Description: BACKGROUND OF THE INVENTION The present invention relates to a degreasing method for metal materials such as iron, zinc, aluminum and the like, and alloyed materials of these. In detail, the invention relates to a method far degreasing a metal surface etc. by using a degreasing solution which shows a very low foaming character and excellent degreasing capability as well as which does not contain a phosphorous compound that may badly affect environment. Hitherto, in the field of metal surface processing, especially in that of metal processing industries, in advance of the conversion coating process by zinc phosphate and the like , degreasing treatment is applied for a matter to be processed to remove oil and fat ( for example, a mineral oil, animal and vegetable oils etc. ) attaching with the matter surface. Since the degreasing process is not a final one and carried out prior to processing such as conversion coating process, an ingredient in the degreasing solution such as remaining by itself or as its reaction product on the surface of a matter to be processed and thereby, badly affecting the conversion coating process is not suitable. In general, the degreasing solution has been adopted such as containing a builder having an acid or alkali as a main body and also, containing a nonionic type or an anionic type surfactant as a main ingredient. The phosphates such as an alkali metal phosphate or alkali metal condensed phosphate or the like have been used as an useful builder to assist the degreasing capability. Recently, it has been pointed out that the phosphates cause eutrophication and pollution in a lake and marsh. Accordingly, in the degreasing of a metal surface, there has been desired the development of a degreasing solution, in which any phosphate is not combined. On the other hand, there is increasing the case where a matter to be processed, like an automobile body, consists of two kinds or more of metal materials such as a composite structure material, which contains not only an iron material and a zinc alloy material, but also an aluminum alloy material. Like this, in a case where a matter to be processed consists of two or more kinds of metal materials is degreased, the formulation of the degreasing solution and processing conditions must be chosen so as to be processed excellently in conversion coating process. An example of a degreasing solution consisting of no phosphate is not combined, has been disclosed in Japanese Examined Patent Publication, showa 61-25784. This degreasing solution is an alkaline degreasing composition consisting of a nonionic surfactant, builder, hydrosulfite and succharide. If a calcium or magnesium salt is brought into this degreasing solution, deterioration of the degreasing capability occurs. Also, if the aforementioned composite structure material is degreased by this degreasing solution, it is not excellently processed in conversion coating process. A method of degreasing with which the aforementioned composite structure material can have an excellent conversion coating performance has been proposed in Japanese Official Patent Provisional Publication, showa 62-199787. This method comprises, when a matter to be processed is processed by an alkali silicate-based degreasing agent, controlling a degreasing solution so as to have its pH at 10.5 or more and to keep the combined Si concentration satisfactorily for the following equation ( a ). However, the degreasing solution used in this method is added with a phosphate as an alkali builder. When this degreasing solution does not contain the phosphate, it does not display sufficient degreasing capability. Meanwhile, in a case where a spraying method is adopted in the processing facilities of metal surface degreasing of this sort, the degreasing solution must be of an especially low foaming character. Conventional degreasing solutions comprise low foaming surfactant such as disclosed in Japanese Examined Patent Publication, showa 36-4373 and Japanese Official Patent Provisional Publication, showa 54-86508. In Japanese Examined Patent Publication, showa 36-4373, surfactants denoted by the following general formula ( 1 ) and in Japanese Official Patent Provisional Publication, showa 54-86508, surfactants denoted by the following general formula ( 2 ) are, respectively, used. [ in the formula, R', EO, and PO denote an alkyl group, ethylene oxide group, and a propylene oxide group, respectively, and m and n show an added mole number. ] [ in the formula, X denotes a hydrogen atom or a hydroxyl group, R¹ and R² denote a hydrogen atom or a methyl group, AO denotes an alkylene oxide group, and p shows an added mole number. ] SUMMARY OF THE INVENTION Not only the single use of surfactants represented by the formulae of ( 1 ) and ( 2 ), but also their combination use with various kinds of builders other than phosphates can not display the excellent degreasing capability continuously. Alkylates of nonylphenol, that are representative examples of the above formula ( 1 ), have been pointed out to show fish-toxicity in their decomposition products and the toxicity is stronger than that of the compounds before decomposition, so that their use in detergents for household use is regulated, and in the field of detergents for industrial use, their use is being regulated. Therefore, there has been desired the combination of a surfactant, which shows excellent degreasing capabiltiy by being combined with various kinds of builders showing a low foaming character and not containing a phosphate, as well as which is not afraid of bad effects upon environment. It is an object of the present invention to provide a degreasing method, which does not comprise any phosphate that may badly affect environment, and which shows a low foaming character and excellent degreasing capability as well as assist good conversion coating performance, when it is applied for a structure material consisting of one kind or more of metal materials among iron, zinc, aluminum, and alloys containing two kinds or more of these metals. To solve the above object, the present invention provides, preferably, a method for degreasing a metal selected from the group consisting of iron, zinc, aluminum and any alloy comprising at least two of these metals, said method comprising bringing a phosphate-free degreasing solution in contact with said metal to be processed under a temperature in a range of 20 - 60°C for a time in a range of 1 to 30 minutes, wherein said degreasing solution contains an alkali silicate, a water-soluble polycarboxylate and a nonionic surfactant and satisfies the following 1 ○ , 2 ○ , 3 ○ and 4 ○ conditions: 1 ○ the pH value of the degreasing solution is in a range of from 10.5 to 12.5; 2 ○ the concentration of said alkali silicate is 100 ppm or more calculated as Si concentration and satisfactory for the following (a) equation: log₁₀Y ≦ 0.318 X + 2.72 (a) wherein Y denotes the concentration of said alkali silicate calculated as Si concentration by a ppm unit, X=pH-10.5, and this pH denotes the pH value of the degreasing solution; 3 ○ the concentration of said water-soluble polycarboxylate is in a range of from 0.01 to 10 g/litre; and 4 ○ the concentration of said nonionic surfactant is in a range of from 0.01 to 10 g/litre, and after bringing said metal into contact with the phosphate-free degreasing solution, replenishing said alkali silicate, said water-soluble polycarboxylate and said nonionic surfactant and adding a caustic alkali to said degreasing solution to maintain the above 1 ○ , 2 ○ , 3 ○ and 4 ○ conditions for further use with subsequent metals. Preferably, the degreasing solution further satisfies a condition that the free alkali content of said degreasing solution is in a range of 5 to 25 points. Preferably, the degreasing solution initially contains no caustic alkalies. Preferably, the replenishing of the alkali silicate and adding of said caustic alkali are carried out by adding to said degreasing solution an agent A containing 1 to 6% by weight of said alkali silicate (calculated as Si concentration against the total alkali compounds), 20 to 60% by weight of an alkali carbonate (against the total alkali compounds) and 10 to 50% by weight of said caustic alkali (against the total alkali compounds) against the total 100% by weight of the three ingredients. Preferably, the replenishing of the water-soluble polycarboxylate and said nonionic surfactant is carried out by adding to said degreasing solution an agent B containing 5 to 40% by weight of said water-soluble polycarboxylate, 10 to 60% by weight of said nonionic surfactant and 0 to 85% by weight of water against a total 100% by weight of the three ingredients. Preferably, the nonionic surfactant is an adduct compound of an aliphatic alcohol with an alkylene oxide containing ethylene oxide in 50 mole % or more of the alkylene oxide and containing either one or both of the propylene oxide and butylene oxide in less than 50 mole %, and said adduct compound has a cloud point in a range of from 25 to 50 °C. The degreasing solution used in this invention contains an alkali silicate, a water-soluble polycarboxylate and nonionic surfactant and, even in a case of not containing a phosphate, it shows a low foaming character and excellent degreasing capability. The pH value of the degreasing solution of this invention is required to be 10.5 or more and its preferable range is 10.5 or more to 12.5 or less ( 10.5 ≦ pH ≦ 12.5 ). If the value is less than 10.5, there occurs the undermentioned problem and, if it exceeds 12.5, an aluminum material is etched in excess and the conversion coating process may be badly affected. In order to maintain the pH value of a degreasing solution at 10.5 or more, a ingredient to assist the pH is added in degreasing solution in addition to the aforementioned essential ingredients. Preferable ingredients of this type are, for example, alkali carbonates such as sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate and the like; caustic alkali such as sodium hydroxide, potassium hydroxide and the like; and these compounds are used alone or in combination of two kinds or more. Preferable alkali silicates used in this invention are, for example, alkali metal salts of orthosilicic acid such as sodium orthosilicate, potassium orthosilicate and the like; alkali metal salts of metasilicic acid such as sodium metasilicate, potassium metasilicate and the like; alkali metal salts of sesquisilicic acid such as sodium sesquisilicate, potassium sesquisilicate and the like; and these compounds ore used alone or in combination of two kinds or more. The concentration of an alkali metal salt of silicic acid used in this invention is required to be 100 ppm or more upon converting into the Si element. If the concentration or an alkali metal salt of silicic acid is less than 100 ppm upon converting into Si, there is a problem mentioned below. However, there is a problem, if the concentration is too high, and it is required to maintain the relationship between the concentration and the pH value of a degreasing solution so as to be satisfactory for the above-described equation ( a ). The water-soluble polycarboxylate used in this invention is not especially limited, as far as it is soluble in water of 0°C or a higher temperature in an amount of 0.01 g per liter or more. A preferable polycarboxylate of this type has the weight-average molecular weight in a range of from 5,000 to 100,000, and a more preferable one has that in a range of from 10,000 to 100,000. The water-soluble polycarboxylate used in this invention is a mono polymer or a copolymer of unsaturated carboxylic acids having one polymerizable double bond, and preferable polycarboxylate is a salt, carboxylic groups of which is neutralized by an alkali metal such as sodium, potassium and the like. If the weight average molecular weight of a polycarboxylate is less than 5,000 or exceeds 100,000, the degreasing capability does not suffficiently rise and may deteriorate with the passage of time. It is required to maintain the concentration or a water-soluble polycarboxylate in a degreasing solution in a range of from 0.01 to 10 g per liter. If the concentration of a water-soluble polycarboxylate is less than 0.01 g per liter, the degreasing capability does not suffficiently rise and may deteriorate with the passage of time. If the concentration exceeds 10 g per liter, a consuming amount of the degreasing solution increases by that the solution enriched in viscosity attaches with a matter to be processed and, in addition, there is an economical disadvantage with no elevation of effects. The water-soluble polycarboxylate is commercially available and, for example, the following goods can be obtained and used for this invention. Products of BASF Co., Ltd. " Sokalan ( registered trademark ) CP-5 " ( a resin solution containing 40 % by weight of a sodium salt of a maleic acid-acrylic acid copolymer having 70,000 in weight average molecular weight ) " Sokalan ( registered trademark ) CP-7 " ( a resin solution containing 40 % by weight of a sodium salt of a maleic acid-acrylic acid copolymer having 50,000 in weight average molecular weight ) " Sokalan ( registered trademark ) PA-40 " ( a resin solution containing 40 % by weight of sodium polyacrylate having 15,000 in weight average molecular weight ) Products of Kao Co., Ltd. " Poiz ( registered trademark ) 520 " ( a resin solution containing 40 % by weight of a specific polycarboxylate ) " Poiz ( registered trademark ) 521 " ( a resin solution containing 40 % by weight of a specific polycarboxylate ) " Poiz ( registered trademark ) 531 " ( a resin solution containing 40 % by weight of a specific polycarboxylate ) Products of Asahi Denka Kogyo Co., Ltd. " Adekacol W-193 " ( a resin solution containing 25 % by weight of a sodium salt of a diisobutylene-olefin-maleic anhydride copolymer ) " Adekacol W-304 " ( a resin solution containing 40 % by weight of sodium polyacrylate ) " Adekacol W-370 " ( a resin solution containing 40 % by weight of a sodium salt of a maleic acid-acrylic acid copolymer ) Examples of the nonionic surfactant used in this invention is such as hitherto-known in public. Among various nonionic surfactants, a preferable surfactant is a monoalkyl ether of polyethylene oxide from a viewpoint that it is superior in degreasing capability and low in fish-toxicity, and another preferable one is a monoalkyl ether of polyethylene oxide polypropylene oxide from a viewpoint that it is superior in degreasing capability, low in fish-toxicity, and superior in a defoaming character ( low foaming character ). Among these monoalkyl ethers, preferable is a nonionic surfactant which is an adduct of an aliphatic alcohol with an alkylene oxide, and in which 50 mole % or more of the alkylene oxide is ethylene oxide, less than 50 mole % is either one or both at propylene oxide and butylene oxide, and the cloud point is in a range of from 25 to 50°C. If the cloud point of the nonionic surfactant is less than 25°C, the degreasing capability is not enough and, if it exceeds 50 °C, the foaming character rises, so that there occurs a problem in the use in spray facilities. An adduct of an aliphatic alcohol with an alkylene oxide such as mentioned above is, for example, a compound shown by the following general formula ( b ). R - O - ( EO ) k ( PO ) l H ( b ) [ in the formula, R denotes an alkyl group of from 8 to 18 in carbon number, EO denotes an ethylene oxide group, PO denotes either one or both of a propylene oxide group and butylene oxide group, k is an added mole number in a range of from 8 to 15, and l is an added mole number in a range of from 1 to 5. ] In the above ( b ) formula, R denotes an alkyl group of from 8 to 18 in carbon number and it may be a straight chain type or a branched type. If the carbon number of R is less than 8 or exceeds 18, the degreasing capability may deteriorate. If the added mole number of ethylene oxide is less than 8, the degreasing capability may deteriorate, and if it exceeds 15, the defoaming character may become bad. If the added mole number of either one or both of the propylene oxide group and butylene oxide group is 0, the defoaming character becomes bad, so that it may take much time to rinse the degreasing solution by water. If the added number exceeds 5, the degreasing capability may decrease. Furthermore, the total of added mole number of the ethylene oxide group and either one or both of the propylene oxide group and butylene oxide group is preferably in a range of from 9 to 20. Nonionic surfactants which are adducts of aliphtic alcohols with alkylene oxides as described above are commercially available and, for example, the under-describerd goods can be obtained and used in this invention. Products of BASF Co., Ltd. " Plurafac ( registered trademark ) LF-220 " ( cloud point 41°C ) " Plurafac ( registered trademark ) LF-400 " ( cloud point 32°C ) In the degreasing solution used in this invention, one kind or two or more kinds of a nitrite, an antiseptic may be properly combined in addition to the aforementioned essential ingredients. Although the content of these optional ingredients differs depending upon the sort, preferable content is in a range of from 0.01 to 1 g per liter. If the content is lower than the range, the additive effect may not emerge, and if it is over, the object of this invention may not be attained. The degreasing solution used in this invention, to maintain its ingredients and concentration, are supplemented with an alkali silicate, a caustic alkali carbonate, water-soluble polycarboxylate and nonionic surfactant. When a suplimentary ingredient is added to maintain the free alkali content in a range of from 5 to 25 points, formulation of the undermentioned agent A is decided so as to put the Si concentration and pH of the degreasing solution in a range defined in this invention and thus, a supplying proportion of the agent B to the agent A is decided. The Si concentration can be grasped by atomic absorption spectrometry, the water-soluble polycarboxylate is quantitatively determined by liquid chromatography etc. and the nonionic surfactant by phosphorus molybdic acid method. One example of the supplimentary ingredient is as follows. agent A: 1 to 6 % by weight of an alkali silicate ( upon converting into Si against the total alkali compounds ) 20 to 60 % by weight of an alkali carbonate ( against the total alkali compounds ) 10 to 50 % by weight of an caustic alkali ( agaist the total alkali compounds ) agent B: 5 to 40 % by weight of an water-soluble polycarboxylate 10 to 60 % by weight of a nonionic surfactant 0 to 85 % by weight of water ( % by weight of A and agent B is a numeral value against the total 100 % by weight of the three ingredients ) The supplementation of agent A is carried out so as to maintain the free alkali content of a degreasing solution in a range of from 5 to 25 points. If the free alkali content of a degreasing solution is less than 5 points, pH of the degreasing solution becomes a value of less than 10.5, so that deterioration of the degreasing capability with the passage of time as well as deterioration of a converting character and coating character of a matter to be processed may be brought about. If the free alkali content of a degreasing solution exceeds 25 point, the effects obtained in the range of from 5 to 25 point which is defined by this invention can not be obtained and the consuming amount of ingredients in the degreasing solution will increase without effects. Here, the free alkali content is denoted in points, a point being an amount ( ml ) of a 0.1 N hydrochloric acid ( or sulfuric acid ) required by neutralizing 10 ml of the degreasing solution using phenolphthalein as an indicator. The content % of a caustic alkali which has in the total alkali ingredients of the agent A is decided in a range of from 10 to 50 % by weight. If the content of a caustic alkali is less than 10 % by weight, even if the agent A is supplemented to maintain the free alkali extent of the degreasing solution in a range of from 5 to 25 points, it becomes difficult to maintain the equibrium pH of the degreasing solution at 10.5 or more or to maintain the degreasing solution composition satisfactory for the above-described ( a ) equation and, thereby, deterioration of the degreasing capability with the passage of time as well as deterioration of a converting and a coating character of a matter to be processed may occurs. Also, if the content of a caustic alkali exceeds 50 % by weight, and when the agent A is supplemented to maintain the free alkali content of the degreasing solution in the aforementioned range, the concentration of a silicate in the degreasing solution decreases with the passage of time and the degreasing capability may decrease compared with the initial stage. The concentration of an alkali silicate in the total alkali ingredients of the agent A is decided in a range of from 1 to 6 % by weight upon converting into the Si element. If the concentration of an silicate exceeds 6 % by weight, it becomes difficult to maintain the degreasing solution composition satisfactory for the above-described ( a ) equation, and thereby, deterioration of convertion coating and paint performance of a matter to be processed may occurs. Also, if the silicate concentration is less than 1 % by weight, even if the agent A is supplemented to maintain the free alkali content of the degreasing solution at a range of from 5 to 25 point, the concentration of a silicate in the decreasing solution decreases with the passage of time and the degreasing capability may deteriorate with the passage of time. Ingredients in the agent A may be supplemented to the degreasing solution alone, respectively, but their supplimenting proportions are desired to be in the aforementioned proportions. Also, to maintain the concentrations of a water-soluble polycarboxylate and a nonionic surfactant in the degreasing solution, the agent B in supplemented. The respective content percents of ingredients in the agent B may be properly choosen corresponding with the respective controlled concentrations in the degreasing solution. Supplementation of the agent B may be carried out by analysing the concentrations of respective ingredients in the degreasing solution and according to the reducing amounts of ingredients, but for the sake of convenience, it is carried out with a constant amount ratio against the aforementioned supplementation of the agent A. The degreasing method of this invention may be carried out similarly to a common degreasing method. For example, there is adopted a processing condition comprising a temperature in a range of from 20 to 60 °C and a time in a range of from 1 to 30 minute. If the temperature is lower than 20 °C, or if the time is less than 1 minute, degreasing capability may become insufficient, and if the temperature exceeds 60°C, or if the time is longer than 30 minutes, the conversion coating performance of a zinc material may decrease. Preferable methods to bring the degreasing solution in contact with a matter to be processed are, for example, an immersing method, a spraying method, and a solution-contact method which consists of combination of here-mentioned methods. On a metal surface degreased by a degreasing solution containing an alkali silicate, a water-soluble polycarboxylate and nonionic surfactant, pH of which is 10.5 or more and in which the Si content and pH value are maintained in a range satisfactory for the above-described ( a ) equation relationship, an excellent quality crystalline film of zinc phosphate ( the 151 type crystal face is many by a X-ray diffraction method ) is formed by subsequent conversion coating process. On the other hand, on a metal surface degreased under a condition deviated from the range of the above-described ( a ) equation, even if its pH is less than 10.5 or it is 10.5 or more, a zinc phosphate film having a lot of 020 type crystal faces of inferior quality is formed by conversion coating process. Further, if the degreasing is continued at a pH of less than 10.5, especially in a case of being processed in a low temperature range of from room temperature to 50 °C or less as carried out in the present invention, the contained surfactant has a decomposing trend and the degreasing capability deteriorates with the passage of time. An excellent degreasing character is obtained by maintaining the concentration of a water-soluble polycarboxylate in a range of from 0.01 to 10 g per liter and the concentration of a nonionic surfactant in a range of from 0.01 to 10 g per liter. A calcium salt or a magnesium salt or the like mingled into a degreasing solution decreases the degreasing capability by its combining with a silicate. Therefore, a builder is added as its dispersing agent, however, in a case where a phosphate is not used, decrease of the degreasing capability still occurs. In the present invention, since a water-soluble polycarboxylate is added to the degreasing solution to maintain its concentration in the aforementioned range, even if a calcium salt or a magnesium salt mingles with the degreasing solution, the decrease of degreasing capability does not occur. According to the present invention, by using a degreasing solution not containing a phosphorus compound which may badly affect environment, a structure material consisting of one kind or more of metal materials among alloys containing iron, zinc, aluminum, or two kinds or more of these metals can be processed with degreasing, which shows a low foaming character and an excellent degreasing character, and thereby, the processed structure material converts into such as having an excellent conversion coating performance. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is illustrated by the following Examples of some preferred embodiments in comparison with Comparative Examples not according to the invention. However, the invention is not limited with the following Examples. -- Example 1 -- A degreasing solution was prepared as shown in the column denoted as " initial " in Table 1. The aforementioned " Sokalan ( registered trademark ) CP-5 " ( a solid portion, 40 % ) is used for a water-soluble polycarboxylate and the " Plurafac ( registered trademark ) LF-220 " for a nonionic surfactant. In a process comprising continuous degreasing treatment, the agent A, that is a supplementary ingredient and made by formulation shown in Table 2 was supplied so as to maintain a free alkali content of the degreasing solution at 15 point and, with supplying the agent B at a proportion of about 30 parts by weight against 100 parts by weight of the agent A, a cold rolled carbon steel sheet, zinc-nickel complex plated steel sheet and an aluminum-magnesium alloy aluminum sheet were degreased. Degreasing and rinsing process Degreasing: immersing method, at 40°C for 2 minutes Rinsing: spraying method, at 15 ∼ 40 °C for 15 seconds As a result or the continuous treatment, three kinds of test slips degreased and rinsed until reaching an equilibrium condition showed an excellent degreasing character and foaming trouble in the degreasing bath and rinsing bath was not observed and, as shown in the column denoted as " in passage of time " in Table 1, great change was not recognized in the solution characteristics. The degreasing capability as well as the foaming character were investigated as described below, and the obtained results are also shown in Table 1. The degreasing capability was examined by a manner which comprises judging by a wetting character ( a water-wetting area percentage ) of the surfaces of three sorts of plates processed by rinsing after the degreasing process, and evaluated by the following standards. o ○ : 100 % of water-wetting ○ : 90 % or more of water-wetting X : less than 90 % of water-wetting The foaming character was examined by a manner which comprises judgment by a foaming condition in a rinsing bath in rinsing after too degreasing process, and evaluated by the following standards. o ○ : Almost no foam was observed on a solution surface of the rinsing bath. ○ : Although a foaming condition was observed on a solution surface of the rinsing bath, there was no case where foam overflowed from the bath having a water temperature of 20°C or higher. X : When a solution temperature in the rinsing bath was 20 °C or lower, the foaming character was strong and a condition of overflowing foam was observed. Each of the test slips degreased and rinsed was processed with a 0.1 % weight/volume solution of Surffine ( registered trademark ) N-5 ( a surface-conditioner, made by Nippon Paint Co., Ltd. ) at room temperature for 15 seconds and then, processed by immersing it in a processing solution of Surfdine ( registered trademark ) SD 2500 ( a Ni-Mn modified zinc phosphate processing agent, made by Nippon Paint Co., Ltd. ) at 40 °C for 2 minutes. Surface-conditioning process Surface-conditioning: immersing method, at room temperature for 15 seconds Conversion coating process Conversion: immersing method, at 40°C for 2 minutes Rinsing: spraying method, at room temperature for 15 seconds Rinsing by deionized water: spraying method, at room temperature for 15 seconds Drying: at 100 °C for 5 minutes On all the conversion coating-processed plates were formed excellent quality crystalline films. Further, on these conversion coating-processed plates, a cationic electrodeposition coating Power Top ( registered trademark ) U-1000 ( made by Nippon Paint Co., Ltd. ) was coated by electrodeposition and baked at 170 °C for 20 minutes. Thickness of the obtained dried films was 35 µm ( hereinafter, the same ). Next, on the plates coated by electrodeposition, an intermediate coating ( " Orga ( registered trademark ) TO4811 grey" , a melamine alkyd resin type, made by Nippon Paint Co., Ltd. ) was coated by spraying so as to make a baked, dried film of 30 µm thickness and then, baked at 140°C for 20 minutes. Next, a top coat ( " Orga ( registered trademark ) TO 630 dover white " , a melamine alkyd resin type, made by Nippon Paint Co., Ltd. ) was coated by spraying so as to make a baked, dried film of 30 µm thickness and then, baked at 140°C for 20 minutes, whereby coated plates of three coat and three bake in total were obtained. These coated plates were subjected to an adhesion test. The adhesion test was carried out by immersing the coated plate in deionized water of 40 °C for 20 days, making checkerboard squares of 1 mm and 2 mm intervals ( 100 pieces ) on the plate by a keen cutter, pasting a tackiness tape on the plate face, peeling off the tape, and counting the number of checkerboard squares remaining on the plate. Adhesion of three kinds of test slips was all excellent. The coating quality was examined by the above-described adhesion test and evaluated by the following standards. o ○ : 100 / 100 squares remained without falling in the test by checkerboard squares of 1 mm interval. ○ : Although falling on a part of the film was recognized in the test by checkerboard squares of 1 mm interval, 100 / 100 squares remained without falling in that of 2 mm interval. X : Falling on a part of the film was recognized in the test by checkerboard squares of 2 mm interval. Results are shown in Table 1. -- Examples 2 to 4 and Comparative Examples 1 and 2 -- The degrasing and rinsing procedure of example 1 was repeated except that control of the degreasing solution was changed as shown in Table 1 and the supplementary ingredients shown in Table 2 were used. Then, similar to the example 1, the conversion coating process and coating were carried out to get coated plates. Similar to the example 1, the degreasing capability, foaming character and coating quality were examined. Results are shown in Table 1. Furthermore, the water-soluble polycarboxylates and nonionic surfactants combined at first with the degreasing solutions in each of the examples and comparative examples were the same as those in the example 1. The " Plurafac ( registered trademark ) LF-700 " is a trade name of an adduct of an aliphatic alcohol with polyethylene oxide polypropylene oxide ( the cloud point is less than 15°C ), made by BASF Co., Ltd., and " Lutensol ( registered trademark ) TO8" is a trade name of isotridecanol octaethoxylate ( the cloud point is 61 °C ), made by BASF Co., Ltd. As seen in Table 1, the results from examples show excellent degreasing capability, a small foaming character and excellent coating quality. In the examples, these three properties are especially superior in the case of using a nonionic surfactant such as an adduct of an aliphatic alcohol with an alkylene oxide, which contains ethylene oxide in 50 mole % or more of the alkylene oxide and contains either one or both of propylene oxide and butylene oxide in less than 50 mole %, and which has a cloud point in a range of from 25 to 50°C ( Examples 1 and 2 ). In contrast, since a water-soluble polycarboxylate is not used in the comparative example 1, the degreasing capability and the coating quality deteriorated with the passage of time. Also, in the comparative example 2, since pH of the degreasing solution is less than 10.5 and not satisfactory for the equation ( a ), the degreasing capability and the coating quality deteriorated with the passage of time.

Claims: A method for degreasing a metal selected from the group consisting of iron, zinc, aluminum and any alloy comprising at least two of these metals, said method comprising bringing a phosphate-free degreasing solution in contact with said metal to be processed under a temperature in a range of 20 - 60°C for a time in a range of 1 to 30 minutes, wherein said degreasing solution contains an alkali silicate, a water-soluble polycarboxylate and a nonionic surfactant and satisfies the following 1 ○ , 2 ○ , 3 ○ and 4 ○ conditions: 1 ○ the pH value of the degreasing solution is in a range of from 10.5 to 12.5; 2 ○ the concentration of said alkali silicate is 100 ppm or more calculated as Si concentration and satisfactory for the following (a) equation: log₁₀Y ≦ 0.318 X + 2.72 (a) wherein Y denotes the concentration of said alkali silicate calculated as Si concentration by a ppm unit, X=pH-10.5, and this pH denotes the pH value of the degreasing solution; 3 ○ the concentration of said water-soluble polycarboxylate is in a range of from 0.01 to 10 g/liter; and 4 ○ the concentration of said nonionic surfactant is in a range of from 0.01 to 10 g/litre, and after bringing said metal into contact with the phosphate-free degreasing solution, replenishing said alkali silicate, said water-soluble polycarboxylate and said nonionic surfactant and adding a caustic alkali to said degreasing solution to maintain the above 1 ○ , 2 ○ , 3 ○ and 4 ○ conditions for further use with subsequent metals. The method for degreasing in accordance with Claim 1, wherein said degreasing solution further satisfies a condition that the free alkali content of said degreasing solution is in a range of from 5 to 25 points. The method for degreasing in accordance with Claim 1 or 2, wherein the degreasing solution initially contains no caustic alkalis. The method for degreasing in accordance with Claim 1, 2 or 3, wherein replenishing of said alkali silicate and adding of said caustic alkali are carried out by adding to said degreasing solution an agent A containing 1 to 6% by weight of said alkali silicate (calculated as Si concentration against the total alkali compounds), 20 to 60% by weight of an alkali carbonate (against the total alkali compounds) and 10 to 50% by weight of said caustic alkali (against the total alkali compounds) against the total 100% by weight of the three ingredients. The method for degreasing in accordance with Claims 1, 2, 3 or 4, wherein replenishing of said water-soluble polycarboxylate and said nonionic surfactant is carried out by adding to said degreasing solution an agent B containing 5 to 40% by weight of said water-soluble polycarboxylate, 10 to 60% by weight of said nonionic surfactant and 0 to 85% by weight of water against a total 100% by weight of the three ingredients. The method for degreasing in accordance with Claims 1, 2, 3, 4 or 5, wherein said nonionic surfactant is an adduct compound of an aliphatic alcohol with an alkylene oxide containing ethylene oxide in 50 mole % or more of the alkylene oxide and containing either one or both of the propylene oxide and butylene oxide in less than 50 mole %, and said adduct compound has a cloud point in a range of from 25 to 50 °C.

Inventors: ISHIDA MINOROU, SHIRAISHI SHOJI, ISHIDA, MINOROU, SHIRAISHI, SHOJI
Applicants: NIPPON PAINT CO LTD, NIPPON PAINT CO., LTD.
Application year: 1992
Main classification: C23G1
IPC codes: C23G1