KR100254533B1 - Composition and process for cleaning tinplate stock - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tin cleaning solution and a cleaning method for the purpose of suppressing Sn sludge generation when cleaning a tin material and performing continuous cleaning.

0.5-10.0 g / L of 1 type (s) or 2 or more types of alkali enhancers chosen from alkali metal hydroxide, an inorganic alkali metal salt or an ammonium salt, an alkali metal borate salt, an alkali metal silicate salt, and an alkali metal carbonate or ammonium salt, and a hydroxide, 0.05 to 1.0 g / l of one or two or more chelating agents selected from oxylalkyldiphosphonic acid, aminotrialkylphosphonic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, condensed phosphoric acid and its alkali metal salts and ammonium salts, Provided are a tin-washing solution and a cleaning method for continuously cleaning a tin-plate with a cleaning solution, which is composed of 0.05 to 2.0 g / l of a surfactant and water and has a pH of 8 to 11.

Description

Tin cleaning material and cleaning method

The present invention is a tin cleaning liquid applied to clean the surface of the tin plate (hereinafter referred to as "tin-plated steel"), plates, strips and molded articles thereof, such as cans (collectively referred to as "tin material") and It relates to a cleaning method. In particular, the present invention is suitable for cleaning of tin DI cans formed by drawing iron and drawing.

In more detail, the present invention is applied to the surface of a tin plate to remove organic substances such as oil and lubricants, inorganic substances such as abrasion powder, etc. from the surface, thereby providing a surface state excellent in chemical conversion treatment and by washing. The present invention relates to a cleaning solution for a new tin material and a method for cleaning the tin material, in which tin eluted from the surface of the tin material to the cleaning liquid becomes an insoluble precipitate.

Regarding the prior art of the cleaning liquid of a tin material, invention of Unexamined-Japanese-Patent No. 59-2752, Unexamined-Japanese-Patent No. 3-59993, Unexamined-Japanese-Patent No. 3-59994 is mentioned.

Alkali cleaning solution of Special Publication No. 59-2752 contains alkali metal silicates and alkali metal salts and alkali metal carbonate salts in a weight ratio of 1.5 times or less, and surfactants in a ratio of 0.4 times or less, As a result, an alkali component called an enhancer is specified as described above so that the tin-plated surface does not overdissolve when the line stops.

Alkaline washing liquid of Japanese Patent Application Laid-Open No. 3-59993 is similar to the above publication for the purpose of preventing excessive dissolution of tin plated surface, and the alkali metal salt or ammonium salt of orthophosphoric acid is 1.5 to 10 g / l and the alkali metal salt of nitrous acid is 0.5 to 2 g / l. Is an aqueous solution containing the former at a molar ratio of 1: 1 to 3.86: 1 and is a liquid adjusted to pH 9 to 11 as an alkali metal carbonate salt.

Alkaline cleaning liquids of Japanese Patent Application Laid-Open No. 3-59994 are similarly used for the purpose of preventing overdissolution of tin-plated noodles, and for the alkali metal salts of orthophosphoric acid or ammonium alkali earth metal oxides, hydroxides, chlorides, bromide, iodides, carbonates, At least one selected from the group of nitrates, sulfates and phosphates is an alkaline aqueous solution having a pH of 9 to 13, containing at least 0.005 g / l and a surfactant, and containing no organic acid or salts thereof.

Cleaning of tinplate is often done by spraying. For example, a surface treatment facility of a tin DI can is usually called a washer and is continuously treated with a cleaning liquid or a chemical liquid in an inverted state of the molded DI can. Conventional washers consist of six steps of pre-cleaning, washing, washing, chemical treatment, washing, and deionized washing, all of which are performed by spraying. Alkaline washing liquid is sprayed into a plurality of DI cans in the above pre-cleaning and washing process, collected in a tank and sprayed again.

In the case where the alkaline washing liquid of Japanese Patent Application Laid-Open No. 59-2752 is actually used for a washer, it can be washed well in the initial stage. Graduate precipitated and precipitated gradually from the washing | cleaning liquid, and these deposits (solids generally called sludge) blocked the pipe | pipe of a spray apparatus and a nozzle, and the thing which cannot wash | clean well happened.

The alkali cleaning solution of Japanese Patent Application Laid-Open No. 3-59993 is described as having high metal solubility when condensation phosphate is present, and deterioration in corrosion resistance in any case after unpainting and painting of tinplate, and condensation phosphate is excluded from the cleaning liquid. Although the dissolution of tin is suppressed, the slightly dissolved tin precipitates as tin phosphate or the like to become sludge, which causes the same problem.

Alkaline washing liquid of Japanese Patent Application Laid-Open No. 3-59994 can be satisfactorily washed at an early stage when actually used. However, tin eluted gradually from tin plate reacts with phosphoric acid or carbonic acid in the washing liquid, and phosphate or carbonate precipitates. And they become sludge.

As described above, the sludge generated by the continuous cleaning causes clogging in the pipe or nozzle of the spray device when a part of the sludge is settled in the tank and a part of the sludge is circulated through the piping system. If the blockage occurs in the pipe or the nozzle, the amount of spray to each DI can decreases, and the method of contacting the liquid becomes uneven, and as a result, good cleaning cannot be performed.

Therefore, in the case of using a conventional alkaline cleaning liquid, the pipes and nozzles of the spray apparatus must be cleaned regularly and frequently. In recent years, the improvement of the productivity of tin plate cleaning is an important problem, and a detergent liquid which reduces the load of these cleanings, that is, does not generate sludge even in continuous use has been desired.

In addition, industrially used alkaline cleaning liquids are disposed of in a manner called small amounts of auto drain periodically or continuously, and are renewed with new cleaning liquids. These discarded washing liquids are discharged through a wastewater treatment process. The above-mentioned conventional alkaline cleaning liquid does not need to be subjected to particularly high wastewater treatment, but is a solid matter (also commonly referred to as "sludge") by wastewater treatment. "Treated sludge").

Conventional alkaline cleaning liquids have a high alkali concentration in the washing, which causes a problem that the throughput of the whole sludge after the waste liquid treatment increases. At present, this sludge is being disposed of as industrial waste, but a reduction in cost and environmental protection is desired.

Moreover, in recent years, the regulation value of effluent water becomes strict in an environmental problem, and the reduction of wastewater treatment load is a big subject.

In order to solve the above-mentioned conventional problems, 0.5 to 10.0 g / of one or more alkali enhancers selected from alkali metal hydroxides, inorganic alkali metal salts or ammonium salts, alkali metal borates, alkali metal silicates and alkali metal carbonate salts or ammonium salts; 0.05 g / 1.0 g / of one or more chelating agents selected from hydroxylalkyldiphosphonic acid, aminotrialkylphosphonic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, condensed phosphoric acid and alkali metal salts and ammonium salts thereof The cleaning liquid for tin plate material which consists of l, 0.05-2.0 g / l of surfactant, and water, and whose pH is 8-11 was discovered, and completed this invention.

That is, the tin cleaning liquid of the present invention removes organic substances such as oil or lubricants, and inorganic powders such as abrasive powders from the surface of tin plates, strips, and molded articles, such as cans, and gives surface conditions excellent in chemical conversion treatment properties. In addition, the amount of sludge precipitated by the hardness component contained in the tin eluted into the washing liquid and the water used in the washing liquid is very small.

Suitable for use of the cleaning liquid of the present invention is the cleaning of DI cans, which include one or two or more alkalises selected from alkali metal hydroxides, inorganic alkali metal salts or ammonium salts, alkali metal borates, alkali metal silicates, and alkali metal carbonate salts or ammonium salts. 0.5 to 10.0 g / l of steel and one or two selected from hydroxylalkyldiphosphonic acid, aminotrialkylphosphonic acid, ethylenediamine tetraacetic acid, nitriloacetic acid, condensed phosphoric acid and alkali metal salts and ammonium salts thereof Spraying a tin cleaning liquid consisting of 0.05 to 1.0 g / l of a chelating agent, 0.05 to 2.0 g / l of a surfactant, and water and a pH of 8 to 11 from a storage tank to a to-be-cleaned tinplate from a nozzle via a pipe. After returning to the storage tank of the tin cleaning liquid, spraying again and without generating sludge of tin and hard water components Clean several DI cans continuously.

In other words, this tin-washing method removes organic matter such as oil or lubricant, inorganic matter such as abrasion powder, etc. from the surface of the DI can, and gives a surface state excellent in image processing property. Long-term continuous cleaning is performed without generating sludge generated by the hardness component contained in the eluted tin and the water used in the cleaning liquid. The presence of sludge is determined by collecting the liquid from the alkaline washing liquid storage tank in a transparent container and visually determining whether the liquid is transparent. In addition, the continuous washing is a process in which sludge does not occur in the continuous treatment under the general treatment conditions such as washing temperature: normal temperature to 80 ° C, spray time: 2 to 60 seconds / canister: liquid update / disposal: 0.04 to 0.08% / 1000 cans. It is possible.

Hereinafter, the composition and washing process of the alkaline cleaning liquid of the present invention will be described in detail.

One or two or more alkali enhancers selected from alkali metal hydroxides, inorganic alkali metal phosphates or ammonium salts, alkali metal borates, alkali metal silicates, and alkali metal carbonate salts or ammonium in the components of the alkaline cleaning solution of the present invention (as component A Content in the Example) is 0.05-10.0 g / L.

In addition, one or two or more compounds selected from hydroxylalkyldiphosphonic acid, aminotrialkylphosphonic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, condensed phosphoric acid and alkali metal salts and ammonium salts of these compounds (implemented as component B) Content in the example) is 0.05-1.0 g / L.

Moreover, content of surfactant (as described in an Example as component C) is 0.05-2.0 g / L. The remainder of the component is water, which is industrial water or water. Moreover, pH of the cleaning solution for tinplate materials is 8-11.

Examples of alkali metal salts of alkali enhancers include potassium or sodium hydroxides, carbonates, borate salts, and inorganic phosphates, and examples thereof include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, borax, and trisodium phosphate. . One kind or two or more kinds thereof are contained, and the concentration thereof is selected so as to have a detergency (etching property) suitable for the state of the tin plate surface. In general, the content of the alkali enhancer is 0.5 to 10.0 g / l, and preferably 1.0 to 5.0 g / l. If it is less than 0.5 g / L, it cannot wash | clean well by lack of etching. Although it can wash | clean favorably even if it exceeds 10.0 g / L, the wastewater treatment sludge produced by wastewater treatment will increase.

Hydroxylalkyldiphosphonic acid, aminotrialkylphosphonic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid and condensed phosphoric acid, and alkali metal salts and ammonium metal salts thereof are added to stably incorporate tin ions incorporated from tinplate materials into the washing liquid. have. In other words, if the tin material is continuously washed, tin ions accumulate in the liquid and react with phosphoric acid, silicic acid, carbonic acid, etc., to generate sludge, but the image material has tin ions as the chelate and tin phosphate in the cleaning liquid. It is to suppress the generation of sludge such as. By suppressing sludge generation, the cleaning load on the pipes and nozzles of the spraying apparatus is greatly reduced.

On the other hand, calcium and magnesium ions contained as hard components in the water do not accumulate in the cleaning liquid as described above, and thus do not interfere with continuous processing. However, calcium and magnesium ions are chelated at the same time by hydroxylalkyldiphosphonic acid and the like. It is not mixed in sludge.

As hydroxylalkyl diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid represented by following Formula is mentioned.

In addition, 1-hydroxypropidene-1,1-diphosphonic acid, 1,1-dihydroxymethylidene-1,1-diphosphonic acid, 2,2- diphosphonic acid propyl alcohol is mentioned.

Moreover, as aminotrialkylpotonic acid, aminotrimethylene phosphonic acid, aminotriethylene phosphonic acid, aminotripropylene phosphonic acid, etc. are mentioned, for example.

Examples of the condensed phosphoric acid include pyrroline acid, tripolyic acid, and tetrapolyic acid.

Hydroxylalkyldiphosphonic acid, aminotrialkylphosphonic acid, ethylenediamine tetraacetic acid, nitric triacetic acid and condensed phosphoric acid can be used for washing liquid with the acid or its alkali metal salt and ammonium salt. Content of 1 type, or 2 or more types of these compounds is 0.05-1.0 g / L, Preferably the range of 0.1-0.5 g / L is good. At less than 0.05 g / l, sludge is easily generated in the cleaning liquid due to lack of chelating force. There is no problem even if it exceeds 1.0g / ℓ, the cost is high, there is a problem economically.

Ethylenediamine tetraacetic acid, nitrile triacetic acid, and condensed phosphoric acid are poor in sedimentation property due to calcined lime (calcium hydroxide), and thus poor wastewater treatment properties. When such wastewater treatment property is a problem, it is good to use hydroxyl alkyldiphosphonic acid and its metal (ammonium) salt having good sedimentation properties similar to slaked lime. In addition, in recent years, eutrophication of rivers and lake swamps is a major problem, and therefore, a detergent that does not contain condensed phosphoric acid is desired. In addition, addition of other chelating agents, for example, organic acids such as gluconic acid or alkali metal salts and ammonium salts thereof, does not impede the effects of the present invention.

Also, in areas where wastewater regulation is particularly stringent, cleaning agents that do not contain phosphorus and nitrogen are useful, so in the present invention, the alkali enhancer is selected from hydroxides, carbonates or borate salts, and hydroxylalkyldiphosphonic acid or aminotrialkyl. If diphosphonic acid is selected, it is also possible to set it as the composition which does not contain phosphorus and nitrogen. Phosphorus is also contained in hydroxylalkyldiphosphonic acid and aminotrialkylsulfonic acid, but as mentioned above, this is not a problem since it is possible to easily settle into calcined lime.

Moreover, the concentration of the alkali salt of the washing | cleaning liquid by this invention is lower than what was shown to the conventional experiment example, and can also be 4 g / L or less. This is because hydroxylalkyldiphosphonic acid and the like have a cleaning effect, and the wastewater treatment sludge generated in the wastewater treatment step can be reduced by reducing the amount of alkali enhancer.

The surfactant is selected from anionic surfactants or nonionic surfactants. For example, as a nonionic surfactant, a hydrocarbon derivative, abies acid derivative, a primary ethoxylated alcohol, and a modified polyethoxylated alcohol are mentioned, and it contains 1 type, or 2 or more types in all. The content is in the range of 0.05 to 2.0 g / L, and preferably 0.2 to 1.0 g / L. If the content is less than 0.05 g / l, organic matter on the surface of the tin plate can not be completely removed. On the other hand, if the content exceeds 2.0 g / l, there is no problem in cleaning, but the cost is high and there is an economic problem.

PH of the washing | cleaning liquid is the range of 8-11, Preferably it is 9-10. If the pH is less than 8, the etching power is low, and it is difficult to clean well, and sludge easily occurs. If the pH is 11 or more, the etching force becomes too strong, which is not preferable such as damaging the appearance. The pH may be adjusted using commercial alkali or acid, ie, sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, or the like, and is not particularly limited.

Although the process temperature of the washing | cleaning liquid of this invention can be from normal temperature to 80 degreeC, it is preferable to heat to 40-60 degreeC normally and to use. The treatment time is 2 to 60 seconds, but less than 2 seconds cannot be sufficiently washed. Even if it is time-processed for more than 60 second, since the improvement of washability cannot be recognized, the processing time is suitable for the range of 2 to 60 second. The treatment method can be either an immersion method or a spray method, but the present invention exhibits particularly excellent effects when used in a spray apparatus as described above.

In the wastewater treatment of the cleaning solution of a tin material, metal ions are dissociated from the chelate compound at an acidic pH, and then solid-liquid separation is performed by addition of calcium hydroxide and a polymer coagulant to obtain wastewater treatment sludge. Since the cleaning liquid according to the present invention has a low alkali concentration, the amount of sludge to be disposed of is reduced. In addition, since hydroxylalkyl disulfonic acid and aminotrialkylsulfonic acid are excellent in settling property by calcium hydroxide and a polymer coagulant, wastewater treatment efficiency is also good.

As described above, tin ions are accumulated in the cleaning of the tin material, and the tin ion concentration in the cleaning liquid when sludge occurs is estimated to be 0.01 to 0.1 g / l. The sludge produced by sedimentation has strong adhesiveness, so it adheres to the nozzle or the pipe and prevents cleaning. As a means of preventing such adhesion, measures to inhibit dissolution of the tin-plated surface and hinder the concentration of tin ions are effective. However, in the case of a large amount of washing, the countermeasures are limited. In addition to the forcing and surfactants, the ingredients added were permanent.

As a result, the surface of the tin plate, strip, and the molded article is cleaned with the cleaning liquid according to the present invention, thereby removing organic matter and inorganic matter from the surface of the tin material, giving a surface state excellent in chemical conversion treatment, and further eluting the cleaning liquid. The amount of sludge produced is very small.

The cleaning liquid of the present invention will be described below with some examples, and its usefulness is shown in comparison with the comparative example.

(1) test materials

Tin cans (66mm) made by tin-plating tin plate Using 1000 pieces of * 124 mmh) as a test material, it wash | cleaned with the washer already installed.

(2) treatment process

The treatment step was in accordance with Step [1] or [2] shown below.

Process [1]

① cleaning

② Water washing (10 second spray)

③ Deionized water washing (10 second spray)

④ Drying (180 ℃, Hot Air)

Process [2]

① cleaning

② Water washing (10 second spray)

③ Chemical treatment (30 seconds spray)

Processing agent: Trademark Falhose K3482, Nippon Park Carizing Co., Ltd.

Concentration: 3% temperature: 60 degrees Celsius

④ Water washing (10 seconds spray)

⑤ Deionized water washing (10 seconds spray)

⑥ Drying (180 ℃, hot air)

(3) Aptitude test method

[Water wettability]

③ of step [1] After the deionization was ended, the can was left for 30 seconds, and the wet area at that time was evaluated in%. Generally 90% or more is good.

[Degreasing property]

Degreasing was evaluated from the amount of oil remaining on the surface. In step [1], the can after treatment is ultrasonically cleaned using carbon tetrachloride, and the oil fraction eluted from the surface of the can into carbon tetrachloride is quantified by an oil content measuring instrument (POC-100, manufactured by Shimadzu Corporation, Japan). It was converted into the residual oil component per unit surface area of. Generally it is good in it being 2 mg / m <2> or less.

[Corrosion resistance]

Corrosion resistance of the can after treatment in step [2] was evaluated by iron exposure degree (IEV). In addition, the measurement of IEV was based on US Patent No. 4332645. The lower the value of the IEV, the better the corrosion resistance, and usually 150 or less is sufficient.

[Paint adhesion]

Paint adhesion is applied to the surface of the can after the process [2] by coating an epoxy urea can with a film thickness of 5 to 7 μm, baking at 215 ° C. for 4 minutes, and forming the can into a rectangular paper of 5 × 150 mm. It cut | disconnected and thermo-compressed with the polyamide film, it was made into the test piece, it peeled by 180 degreeC test method, and it evaluated at the film strength at that time. Therefore, the greater the coating strength, the better the paint adhesion. In general, 1.5kgf / 5mm width or more is good.

[Sludge Generation in Cleaning Liquid]

In the cleaning liquid used for the Example and the comparative example, the thing of the composition which does not contain surfactant was adjusted. 0.1 g / L of tin was added to these washing liquids (two tin chlorides were used, and PM addition was performed with potassium hydroxide after addition), and it was left to stand for 1 day. And the liquid state after that was observed. It is preferable that it is transparent and no precipitation is generated.

Wastewater Treatment

Wastewater treatment was evaluated by the following method. The treatment liquid was diluted to 1/10 equivalent to the dilution degree of treatment liquid wastewater treatment in actual operation, and this liquid was adjusted to pH 2.5 with sulfuric acid. Next, an aqueous solution of aluminum sulfate was added so as to be 20 ppm as aluminium, and the pH was adjusted to 10 with calcium hydroxide. 10 ppm of polymer coagulant was added thereto, and solid-liquid separation was performed. The remaining sludge (solid content) was dried at 110 ° C. for 24 hours and weighed after cooling. At this weight, wastewater treatment was evaluated. That is, it is preferable that the generated weight of sludge is smaller.

Example 1

The washing | cleaning liquid 1 shown below was wash | cleaned for 30 second at 50 degreeC using. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, the sludge generation property and wastewater treatment property of this washing | cleaning liquid 1 were evaluated.

Cleaning liquid (1)

Sodium Carbonate (A) 2.0g / ℓ

Natarium hydrogen carbonate (A) 2.0g / ℓ

Sodium tripolyphosphate (B) 0.4 g / l

Nonylphenol EO-11 mol addition product (C) 0.2 g / L

pH 9.6 (adjusted with sodium hydroxide)

Example 2

The washing | cleaning liquid 2 shown below was wash | cleaned for 30 second using 50 degreeC. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, sludge generation property and wastewater treatment property of this washing | cleaning liquid 2 were evaluated.

Cleaning liquid (2)

Potassium Carbonate (A) 1.0g / ℓ

Potassium Hydrogen Carbonate (A) 2.0g / ℓ

0.2 g / L of 1-hydroxyethylidene-1,1-diphosphonic acid (B)

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.3 g / l

pH 9.6 (adjusted with sodium hydroxide)

Example 3

The washing | cleaning liquid 3 shown below was wash | cleaned for 30 second using 50 degreeC. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, this washing | cleaning liquid 3 evaluated sludge generation property and wastewater treatment property.

Cleaning liquid (3)

Sodium Carbonate (A) 2.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

0.5 g / l ethylenediamine sodium tetraacetate (B)

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.2 g / l

pH 10.0 (adjusted with sodium hydroxide)

Example 4

The washing | cleaning liquid 4 shown below was wash | cleaned for 60 second at 50 degreeC using. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, sludge generation | occurrence | production and wastewater treatment property of this washing | cleaning liquid 4 were evaluated.

Cleaning liquid (4)

Sodium Carbonate (A) 1.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

0.3 g / l 1-hydroxyethylidene-1,1-diphosphonic acid (B)

Nonylphenol EO-11 mol adduct (C) 0.2 g / L

pH 8.7 (adjusted with sulfuric acid)

Example 5

The washing | cleaning liquid 5 shown below was wash | cleaned for 15 second at 40 degreeC using. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, the sludge generation | occurrence | production and wastewater treatment property of this washing | cleaning liquid 5 were evaluated.

Cleaning liquid (5)

Sodium Hydroxide (A) 0.3g / ℓ

Disodium hydrogen phosphate (A) 0.1g / ℓ

0.3 g / l 1-hydroxyethylidene-1,1-diphosphonic acid (B)

Nonylphenol EO-11 mol addition product (C) 0.4 g / L

pH 10.5 (adjusted with sodium hydroxide)

Example 6

The washing | cleaning liquid 6 shown below was wash | cleaned for 60 second at 60 degreeC using. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, the sludge generation property and wastewater treatment property of this washing | cleaning liquid 6 were evaluated.

Cleaning liquid (6)

Sodium Carbonate (A) 1.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

Sodium tripolyphosphate (B) 0.1 g / L

0.3 g / l 1-hydroxyethylidene-1,1-diphosphonic acid (B)

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.4 g / l

pH 8.7 (adjusted with sulfuric acid)

Example 7

The washing | cleaning liquid 7 shown below was wash | cleaned for 60 second at 30 degreeC using. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, sludge generation | occurrence | production and wastewater treatment property of this washing | cleaning liquid 7 were evaluated.

Cleaning liquid (7)

Sodium Carbonate (A) 1.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

Borax (A) 1.0g / ℓ

0.3 g / l 1-hydroxyethylidene-1,1-diphosphonic acid (B)

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.4 g / l

pH 10.2 (adjusted with sodium hydroxide)

Example 8

The composition of the washing | cleaning liquid 2 of Example 1 was changed as follows, and it wash | cleaned like Example 1.

Cleaning liquid (8)

Sodium Carbonate (A) 0.25g / ℓ

Trisodium Phosphate (A) 0.25 g / L

Sodium tetrapolyphosphate (B) 0.05 g / l

Nonylphenol EO 1-1 mole adduct (C) 0.2 g / l

pH 9.6 (adjusted with sodium hydroxide)

Example 9

The composition of the washing | cleaning liquid 1 of Example 1 was changed as follows, and it wash | cleaned like Example 1.

Cleaning liquid (9)

Sodium Carbonate (A) 5g / ℓ

Sodium bicarbonate (A) 5g / ℓ

Phyllolic Acid (B) 1g / ℓ

Nonalphenol EO 1-1 mole adduct (C) 0.2 g / l

pH 9.6 (adjusted with sodium hydroxide)

Example 10

3.0 g / L sodium phosphate was used instead of potassium carbonate and potassium hydrogen carbonate in the washing liquid 2, and the other compositions were the same, and washing was performed in the same manner as in Example 2.

Example 11

3.0 g / L ammonium dioxide was used instead of potassium carbonate and potassium hydrogen carbonate in the washing liquid 2, and the other compositions were the same, and washing was performed in the same manner as in Example 2.

Example 12

3.0 g / L sodium borate was used in place of potassium carbonate and potassium hydrogen carbonate in the washing solution 3, and the other compositions were similarly washed in the same manner as in Example 2.

Example 13

3.0 g / L ammonium carbonate was used instead of potassium carbonate and potassium hydrogen carbonate in the washing liquid 3, and the other compositions were the same, and washing was performed in the same manner as in Example 2.

Example 14

1,1-dihydroxymethylidene-1,1-diphosphonic acid is used instead of 1-hydroxyethylidene-1,1-diphosphonic acid of the washing liquid (2), and the other composition is the same, Cleaning was performed in the same manner as in Example 2.

Example 15

1-hydroxypropidene-1,1-diphosphonic acid was used instead of 1-hydroxyethylidene-1,1-diphosphonic acid of the washing liquid (2), and the other composition was the same, Example 2 Similarly, washing was performed.

Example 16

Instead of 1-hydroxyethylidene-1,1-diphosphonic acid of the washing liquid (2), 2,2-diphosphonic acid propyl alcohol was used. .

Example 17

Cleaning liquid (10)

Sodium Carbonate (A) 1.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

Borax (A) 1.0g / ℓ

Aminotrimethylenephosphonic acid (B) 0.3 g / l

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.4 g / l

pH 10.2 (adjusted with sodium hydroxide)

Cleaning was performed in the same manner as in Example 2 using the cleaning liquid 10.

Example 18

It wash | cleaned similarly using aminotriethylene phosphonic acid instead of the amino trimethylene phosphonic acid of Example 17.

Example 19

It wash | cleaned similarly using aminotripropylene phosphonic acid instead of the amino trimethylene phosphonic acid of Example 17.

Example 20

Cleaning liquid (11)

Sodium Carbonate (A) 1.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

Borax (A) 1.0g / ℓ

0.3 g / l nitrile triacetic acid (B)

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.4 g / l

pH 10.2 (adjusted with sodium hydroxide)

It wash | cleaned similarly to Example 2 using the washing | cleaning liquid 11.

Comparative Example 1

The washing | cleaning liquid 12 shown below was wash | cleaned for 30 second using 50 degreeC. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, the sludge generation property and wastewater treatment property of this washing | cleaning liquid 12 were evaluated.

Cleaning liquid (12)

Sodium Carbonate (A) 1.0g / ℓ

Sodium bicarbonate (A) 2.0g / ℓ

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.4 g / l

pH 9.6 (adjusted with sodium hydroxide)

Comparative Example 2

The washing | cleaning liquid 13 shown below was wash | cleaned for 30 second using 50 degreeC. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, the sludge generation property and wastewater treatment property of this washing | cleaning liquid 13 were evaluated.

Cleaning liquid (13)

Potassium Carbonate (A) 1.0g / ℓ

Potassium Hydrogen Carbonate (A) 2.0g / ℓ

0.2 g / l of 1-hydroethylethylidene-1,1-diphosphonic acid (B)

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.4 g / l

pH 7.5 (adjusted with sulfuric acid)

Comparative Example 3

The washing | cleaning liquid 14 shown below was wash | cleaned for 60 second at 60 degreeC using. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, the sludge generation property and wastewater treatment property of this washing | cleaning liquid 14 were evaluated.

Cleaning liquid (14)

Sodium metasilicate (A) 2.5 g / l

Sodium Carbonate (A) 2.5g / ℓ

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.3 g / l

Higher alcohol EO-5 mol, PO-10 mol adduct (C) 0.3 g / l

pH 11.0 (adjusted with sodium hydroxide)

[Comparative Example 4]

Washing | cleaning was performed at 50 degreeC for 30 second using the 1% washing liquid of tin DI can cleaner (trade name Fine Cleaner 4361A Nippon Park Carizing Co., Ltd.) which contains a commercially available alkali enhancer and surfactant as an active ingredient. And water wettability, degreasing property, corrosion resistance, and paint adhesiveness were evaluated. Moreover, sludge generation property and wastewater treatment property of this washing | cleaning liquid were evaluated.

Example 21

The same results were obtained when the respective acids were used in place of the condensed phosphates of Examples 1 and 6.

Example 22

Instead of sodium tripolyphosphate of the washing liquid (1), 0.2 g / l pyrroline acid, 0.2 g / l tripolyic acid and 0.1 g / l tetrapolylinic acid were used, respectively. The same result as in Example 1 was obtained.

As is apparent from the above-described examples and comparative examples, the present invention provides the same general cleaning performance as that of the conventional sludge-plating DI can, such as water wettability, degreasing resistance, corrosion resistance, adhesion, and the like. Suppression and wastewater treatment are superior to the prior art.

Moreover, although the Example of cleaning DI can was demonstrated in the Example, it is clear that the same response is also exhibited with the tin plate and strip which are other molded articles and raw materials. Therefore, the present invention has a very excellent effect of reducing the burden of waste water treatment while increasing the cleaning ability of the tin material.

Claims (3)

0.5-10.0 g / l of one or more alkali enhancers selected from alkali metal hydroxides, inorganic alkali metal salts or ammonium salts, alkali metal borates, alkali metal silicates, alkali metal carbonates or ammonium salts, and hydroxyalkyl diphosphone 0.05 to 1.0 g / l of one or two or more chelating agents selected from acids, aminotrialkylphosphonic acids, ethylenediamine tetraacetic acid, nitrile triacetic acid, condensed phosphoric acid and alkali metal salts and ammonium salts thereof, Tin-washing solution for a tin material, characterized in that consisting of 0.05 to 2.0 g / l, and water, and the pH is 8-11. The tin-washing solution according to claim 1, wherein the chelating agent is one or two or more of hydroxylalkyldiphosphonic acid and aminotrialkylphosphonic acid, and alkali metal salts and ammonium salts thereof. 0.5 to 10.0 g / l of an alkali enhancer selected from alkali metal hydroxides, inorganic alkali metal salts or ammonium salts, alkali borate metal salts, alkali silicate metal salts, and alkali metal carbonate salts or ammonium salts, and hydroxylalkyl diphosphone 0.05 to 1.0 g / l of one or two or more chelating agents selected from acids, aminotrialkylphosphonic acids, ethylenediamine tetraacetic acid, nitrile triacetic acid, condensed phosphoric acid and alkali metal salts and ammonium salts thereof, A tin cleaning solution consisting of 0.05 to 2.0 g / l and water and having a pH of 8 to 11 is sprayed from the storage tank to the to-be-cleaned tin material from the diesel oil nozzle, and returned to the storage tank of the tin cleaning liquid and sprayed again. The tin-plate cleaning method characterized in that the tin plate is continuously washed without generating sludge of tin and hard water.