[1]The invention washing compositions used in the pickling process, which relates to a washing method for pickling steel washing composition and pickling the steel sheet using the same of, and prevent yellowing caused the steel plate surface after pickling is screen property surface so that quality can be obtained a steel sheet excellent and it relates to a washing method using the same.
[2]Furthermore, the present invention relates to a steel sheet subjected to the water washing step.
BACKGROUND
[3]
The surface of the steel sheet is exposed to generally at a high temperature after annealing the hot-rolled steel sheet subjected to hot rolling, a portion of the cold-rolled steel sheet subjected to water-cooling in the continuous annealing step after the cold rolling, or a predetermined time or more air are formed in the coating various types of oxides. The oxide film is removed from the pickling process, because it decreases the quality of the later process.
[4]
[5]
Wherein the pickling step has been included with a drying step for removing moisture that has accumulated during water washing step and washed with water to remove the acid solution that has accumulated in the pickling step to remove the oxide film of the steel sheet surface with an acid solution, the pickling when a steel sheet. However, the steel sheet surface is oxidized again in the washing step and the drying step, changing the dark surface of the steel sheet, there is a problem that yellowing occurs.
[6]
[7]
In particular, high strength steel, because generally contain a lot of strong acid chemical conversion elements such as manganese, silicon, aluminum and magnesium are likely to occur due to yellowing reoxidation. In particular, the manganese is not less than 1.0% by weight of the steel sheet to display the yellowing exacerbate.
[8]
[9]
Since this acts as a factor that the oxide film formed on the surface of the steel sheet after pickling is deteriorated as the subsequent step of phosphate, plating or coating quality is a technique for preventing the yellowing of the surface of the steel sheet after pickling is required.
[10]
[11]
Representative methods for the prevention of the yellowing of the conventional pickling process may include techniques such as described in KR2000-0082171, KR2006-0079405, US2002-201705, JP2001-319765.
[12]
[13]
The KR2000-0082171 discloses a technique for preventing a hot-rolled steel sheet is described by corrosion in the water washing step, by neutralization and washing of the pH with sodium hydroxide. On the other hand, KR2006-0079405 are alkyl amines, alkyl diamines, alkyl tetra one or more than one volume is 40 to 80% of the amine, as a high temperature stabilizer, a photo-tetrahydro-1,4-oxide and 10 to 50% by volume and the aqueous solution of stabilizing agent as it has been providing stains and rust inhibitor of pickling the steel sheet containing the anhydrous citric Acid 10% by volume or more.
[14]
[15]
Further, US2002-201705 are gluconate and discloses a technique for floating Polyquaternium the surface was treated with an aqueous solution of a titanium compound Taehwa, JP2001-319765 is by a carboxylic acid and an alkali agent in the reaction of the discoloration preventing subsequent treatment tank after the pickling processing the color transfer inhibitors generated, and discloses a technique of removing the color transfer inhibitor in the subsequent washing tub.
[16]
[17]
However, the technique described in the prior literature are not satisfactory capability prevents yellowing, in particular, yellowing room intelligence for the high-strength steel as described above is not more enough.
[18]
[19]
Thus, when the anti-yellowing to provide a washing composition and a washing method using the same in the surface quality of the steel sheet can be improved is expected to be applied widely in the art.
[20]
Detailed Description of the Invention
SUMMARY
[21]
Thus, one aspect of the present invention is to provide a washing composition of pickling the steel sheet can be obtained having excellent surface quality of the steel sheet by re-oxidation to prevent the surface of the steel sheet after pickling inhibit yellowing occurs.
[22]
[23]
Another aspect of the present invention to provide a washing method of this pickling steel sheet using a washing composition of the present invention as.
[24]
[25]
In addition, the present invention is to provide a process within the yellowing of the steel sheet in the washing stage of the pickling process in order to prevent yellowing caused the screen the surface of the steel sheet after pickling property.
[26]
Problem solving means
[27]
The present invention provides a washing composition of pickling the steel sheet as one aspect, washing compositions 6 to 14% by weight of phosphoric acid ester compound, an amine-based compound of 6 to 19% by weight provided by the invention, 1 to 9% by weight sodium carbonate, ammonium acetate, 1 to 9% by weight, the EDTA containing water (ethylenediaminetetraacetic acid), 1 to 14% by weight and the balance.
[28]
[29]
The present invention relates to a light other things, provides a washing composition of pickling the steel sheet, the washing composition is from 15 to 24% by weight of phosphoric acid ester, citric acid 5 to 15% by weight, 2 to 10% by weight of sodium carbonate, sodium acetate 2-7 % by weight, and DTPA (diethylene tetramine pentaacetic acid) 1 to 7% by weight, and the balance comprising water.
[30]
[31]
The phosphoric ester compounds in each of the washing composition as bisphenol A- bis (diphenyl phosphate), triaryl phosphate, isopropyl, dimethyl methyl phosphate, tetraphenyl-m- phenylene bis (phosphate), triethyl phosphate and triphenyl phosphate is at least one member selected from the group consisting of compounds.
[32]
The amine-based compound is at least one compound selected from the group consisting of ethylamine, methylamine, propylamine, butylamine, polyethylene amine, polypropylene amine, polybutyl amines, and poly arylamine.
[33]
Wherein the washing composition in each water washing composition is preferably not less than pH 8.0, more preferably a pH of 8.5 to 11.5.
[34]
Each of the washing composition can be diluted in water in an amount of 0.05 to 1.5% by weight.
[35]
[36]
The invention still another aspect provides a washing method for pickling steel, wherein the washing method is 6 to 14% by weight of phosphoric acid ester compound, an amine-based compound of 6 to 19% by weight, 1 to 9% by weight sodium carbonate, ammonium acetate 1 to 9% by weight, and mixing to prepare a water washing composition of pickling the steel sheet for EDTA 1 to 14% by weight and the balance of water, comprising the washing composition of the immersion step and pickling the steel sheet, which is diluted in water to the washing composition do.
[37]
[38]
Washing method according to another aspect of the present invention is 15 to 24% by weight of phosphoric acid ester, citric acid 5 to 15% by weight, 2 to 10% by weight of sodium carbonate, sodium acetate, 2 to 7% by weight, DTPA (diethylene tetramine penta acetic acid) 1 to 7 wt% and mixed with the balance of water and washed with water to prepare a composition of the pickling steel sheet, comprising the steps of diluting said composition in water, washed with water, and pickling the steel sheet and a step of immersing in the washing composition.
[39]
The method comprising the washing composition being diluted in water in each of the washing method is performed by diluting in water the washing composition in an amount of 0.05 to 1.5% by weight.
[40]
Wherein the phosphoric acid ester compounds in each of the washing method is a bisphenol A- bis (diphenyl phosphate), triaryl phosphate, isopropyl, dimethyl methyl phosphate, tetraphenyl-m- phenylene bis (phosphate), triethyl phosphate and triphenyl phosphate 1 is at least one compound selected from the group consisting of.
[41]
The amine-based compound is at least one compound selected from the group consisting of ethylamine, methylamine, propylamine, butylamine, polyethylene amine, polypropylene amine, polybutyl amines, and poly arylamine.
[42]
Wherein the washing composition in each water washing method is preferably not less than pH 8.0.
[43]
[44]
In yet another aspect the invention provides a process in yellow plate, as the steel sheet is steel sheet containing not less than 1.0% by weight Mn, 0.01 ~ 5㎎ / ㎡ of P as a component other than the steel components on the surface of the steel sheet after pickling and washing with water 0.01 to contain 500㎎ / ㎡ of C and 0.1 ~ 500㎎ / ㎡ O.
[45]
The steel sheet is more than 55 yellowness index of 4.0 or less, and whiteness.
[46]
Except for the steel components to the steel sheet surface and from the N, F, Na, Al, Si, S, K, Ca, Ti, V, Cr, Mn, Co, Ni, the group consisting of Cu, Cl, Zn, Zr and Mo at least one component selected from 0.01 to may further contain 5㎎ / ㎡.
[47]
The steel sheet may contain Ni or a Zn plated layer made of a Ni flash plating or Zn flash plating.
[48]
The steel sheet may comprise a phosphate-treated layer according to the phosphating solution.
[49]
The steel sheet may include a plated layer by hot dip coating or electroplating, including at least one component of the Zn, Al, Mg, and Si.
[50]
The steel sheet may comprise a resin layer of the resin composition is applied.
[51]
The steel sheet may be a rust preventive oil is applied.
[52]
Effects of the Invention
[53]
According to the present invention, in the pickling process of the steel sheet remarkably improved by yellowing room intelligence, even during the production of steel and oxidation resistance containing group and class high-strength steel sheet with a lot of components it is possible to obtain a good surface quality without yellowing.
[54]
[55]
According to the present invention, and in the oxidation-resistant steel high-strength steel sheet, which contains a lot of components, the yellowing occurring in the pickling process of the steel sheet is prevented, resulting in that with improved surface quality of the product and of the various subsequent processes them effects can be obtained.
[56]
Best Mode for Carrying Out the Invention
[57]
Hereinafter, a preferred embodiment of the present invention. However, embodiments of the present invention can be modified in many different forms and is not limited to the embodiments and the scope of the present invention described below.
[58]
[59]
Surface of generally the steel is exposed to generally at a high temperature after annealing the hot-rolled steel sheet subjected to hot rolling, cold rolling, and then a part of the cold-rolled steel sheet subjected to water-cooling in the continuous annealing process, or a predetermined time or more air after the high temperature heat treatment of the steel sheet has many forms has the oxide film is formed. The oxide film is removed from the pickling process, because it decreases the quality of the later process.
[60]
[61]
The pickling process, including, with a drying step for removing moisture that has accumulated during water washing step and washed with water to remove the acid solution that has accumulated in the pickling step to remove the oxide film of the steel sheet surface with an acid solution, the pickling when a steel sheet, said the surface of the steel sheet is oxidized again in the washing step and the drying step there is a problem in changing the surface of the steel sheet dark. In particular when high strength steel is more heavily brightness reduction due to re-oxidation because it contains a lot of strong acid chemical conversion the steel components such as manganese, silicon, aluminum and magnesium.
[62]
[63]
Thus, the present invention is to prevent a phenomenon in which the surface of the steel sheet after the re-oxidation and yellowing pickling provides a washing composition and a washing method using the same in the pickling process in a surface quality can be obtained a steel sheet excellent.
[64]
[65]
According to one aspect of the present invention the washing composition of the phosphoric acid ester compound, an amine compound, sodium carbonate, ammonium acetate, EDTA (ethylene diamine tetraacetic acid) and the balance pickling steel sheet containing water portion is provided. The washing composition is from 6 to 14% by weight of phosphoric acid ester compound, an amine-based compound of 6 to 19% by weight, sodium carbonate, 1 to 9% by weight of ammonium acetate, 1 to 9% by weight, EDTA 1 to 14% by weight and the balance water It includes.
[66]
[67]
In the present invention, the phosphoric acid ester compound is a bisphenol A- bis (diphenyl phosphate), triaryl phosphate, isopropyl, dimethyl methyl phosphate, tetraphenyl-m- phenylene bis (phosphate), triethyl phosphate and triphenyl phosphate that the at least one member selected from the group consisting of compounds are preferred.
[68]
[69]
When the case where the phosphoric acid ester compound is added in an amount of less than 6% by weight, there is a problem that can not exhibit a sufficient yellowing room INT exceeds 14 wt%, there is a problem that unevenness occurs in the steel sheet during washing. More preferably, it is a phosphoric acid ester compound is contained in an amount of 8 to 12% by weight.
[70]
[71]
In the present invention, the amine compound is ethylamine, methylamine, propylamine, butylamine, polyethylene amine, polypropylene amine, polybutyl amines, and poly preferred that the at least one compound selected from a group consisting of arylamine Do.
[72]
[73]
When the case where the amine-based compound is added in an amount of less than 6% by weight, there is a problem that can not exhibit a sufficient yellowing room intelligence, exceeding 19% by weight, there is a problem that unevenness occurs in the steel sheet during washing. More preferably, it is a phosphoric acid ester compound is contained in an amount of 10 to 14% by weight.
[74]
[75]
The sodium carbonate will precipitate upon washing with water if less than 1% by weight, the component used to adjust the pH of the tax be the composition of the present invention, has a hard-to-control a favorable pH to prevent yellowing problem, exceeding 9% by weight this is a problem that occurs. More preferably the sodium carbonate is contained in an amount of 4 to 8% by weight.
[76]
[77]
When the ammonium acetate is the problem that, the precipitates during water washing occurs if less than the ingredients used to adjust the pH of the tax be the composition of the present invention to improve the solution stability, and 1% by weight, more than 9% by weight effect is saturated and there is a problem that odor is generated. More preferably the ammonium acetate is included in an amount of 3 to 7% by weight.
[78]
[79]
The EDTA (ethylene diamine tetraacetic acid, ethylene diamine tetraacetic acid) is a problem that can not exhibit a sufficient yellowing room intelligence is less than the ingredients used for the yellowing inhibition of and washing composition of the invention, 1 wt%, 14 wt. if it exceeds%, there is a problem that the solution stability decreases. More preferably the EDTA is included in an amount of 6 to 10% by weight.
[80]
[81]
Further, the washing compositions of pickling the steel sheet of the present invention includes a glass of water. That is, the water is the premise composition along with the other components of the washing composition of pickling the steel sheet of the invention is contained in an amount which is 100% by weight. In the present invention, it is preferable that the water using purified water.
[82]
[83]
On the other hand, according to another aspect of the invention, there is provided a washing composition of the phosphoric acid ester compound, citric acid, sodium carbonate, sodium acetate, DTPA (diethylene tetramine penta-acetic acid) and the balance pickling steel sheet comprising a water portion, wherein the washing composition It comprises a phosphoric acid ester compound 15 to 24 wt%, citric acid 5 to 15% by weight, 2 to 10% by weight of sodium carbonate, sodium acetate, 2 to 7% by weight, DTPA 1 to 7% by weight and the balance water.
[84]
[85]
In the present invention, the phosphoric acid ester compound is a bisphenol A- bis (diphenyl phosphate), triaryl phosphate, isopropyl, dimethyl methyl phosphate, tetraphenyl-m- phenylene bis (phosphate), triethyl phosphate and triphenyl phosphate that the at least one member selected from the group consisting of compounds are preferred.
[86]
[87]
When the case where the phosphoric acid ester compound is added in an amount of less than 15% by weight, there is a problem that can not exhibit a sufficient degree of whiteness improved performance, greater than 25% by weight, there is a problem that unevenness occurs in the steel sheet during washing. More preferably, it is a phosphoric acid ester compound is contained in an amount of 18 to 21% by weight.
[88]
[89]
The citric acid is a component to implement a high intensity brightness enhancement Steel, has a sufficient degree of whiteness problem that exhibits improved performance, the precipitate when flushing occurs if it exceeds 15 wt.% When added in an amount of less than 5% by weight there is a problem. More preferably, the citric acid is contained in an amount of 9 to 13% by weight.
[90]
[91]
The sodium carbonate is when there are the ingredients used, is less than 2% by weight is difficult to be adjusted in a favorable pH for improved color problems in order to adjust the pH of and washing composition of the present invention, washing with water, if it exceeds 10% by weight there is a problem that precipitation occurs. More preferably the sodium carbonate is contained in an amount of 4 to 8% by weight.
[92]
[93]
When the sodium acetate to adjust the pH of the tax be the composition of the invention and solution of the ingredients used to enhance the stability, it is less than 2% by weight has a problem that precipitate during flushing occurs, more than 12% by weight of effect that there is a problem that unevenness occurs in the saturated and the steel sheet. More preferably, the sodium acetate is contained in an amount of from 5 to 9% by weight.
[94]
[95]
The DTPA (diethylene tetramine penta acetic acid, diethylene tetramine pentaacetic acid) is a problem that can not exhibit a sufficient degree of whiteness improved performance if the components used for brightness improvement of and washing composition of the invention, less than 1% by weight , there is a problem that the reduced solution stability, if it exceeds 7% by weight. More preferably the DTPA is contained in an amount of 2 to 4% by weight.
[96]
[97]
Further, the washing compositions of pickling the steel sheet of the present invention includes a glass of water. That is, the water is the premise composition along with the other components of the washing composition of pickling the steel sheet of the invention is contained in an amount which is 100% by weight. In the present invention, it is preferable that the water using purified water.
[98]
[99]
Each washing composition of pickling the steel sheet provided by each aspect of the present invention is preferred that the pH is adjusted to reduce the corrosion rate of the steel sheet, and the washing composition, and preferably not less than pH 8.0, more preferably in the washing compositions are those, wherein pH is 8.5 to 11.5.
[100]
[101]
Is less than the pH of the pickling of steel sheet of the invention washing composition is 8.0, there is a problem in that the corrosion rate reduction effect can not be exhibited less yellowing room enough intelligence. On the other hand, in the case of using the washing composition of pickling the steel sheet is not less than pH 8.0 as in the present invention may be enhanced capability prevent yellowing, since the steel sheet may be washed with water at about corrosion area or stable region.
[102]
[103]
The washing compositions of the invention when applied to the washing of pickling the steel sheet, it is preferable to use diluted with additional water, for example, it is diluted in water in an amount of 0.05 to 1.5% by weight. When the concentration of the diluted washing composition of less than 0.05% by weight has a sufficient yellowing problem that can not exhibit the room intelligence, if it exceeds 1.5 wt%, the effect becomes saturated and further adding from an economic point of view means that so large , a non-economic issues.
[104]
[105]
In the washing composition of the present invention can be applied pickling steel sheet, but are not particularly limited, such as a hot-rolled steel pickling process, hot-rolled steel pickling ointment process, hot-rolled steel pickling plating process, a continuous annealing process, the stainless steel process, melt coating process, electro-galvanizing processes may be a steel pickling in any step of pickling the steel, it is not particularly limited.
[106]
[107]
Case of carrying out the water washing in the pickling process using a washing composition of the present invention as described above has excellent whiteness can be obtained steel sheet by inhibiting the yellowing of a high-strength steel sheet.
[108]
[109]
Washing method of pickling the steel sheet of the present invention is a phosphoric acid ester compound, an amine compound, sodium carbonate, ammonium acetate, EDTA (ethylene diamine tetraacetic acid), and the balance water; Or a mixture of a phosphoric acid ester compound, citric acid, sodium carbonate, sodium acetate, DTPA (diethylene tetramine penta-acetic acid) and the balance water to prepare a washing composition of the pickling steel sheet, respectively; Steps of diluting each of the washing composition in water; And pickling the steel sheet and a step of immersion in each of the washing composition.
[110]
[111]
Information on each component and the content of the washing composition in the washing method of pickling the steel sheet of the present invention as described above.
[112]
[113]
Further, it is preferable to dilute the water to each of the washing composition The washing compositions In each as diluted with water in an amount of 0.05 to 1.5% by weight as described above. When the concentration of the diluted washing composition of less than 0.05% by weight can not exert a sufficient yellowing room intelligence, if it exceeds 1.5 wt%, the effect becomes saturated and further adding from an economic point of view does mean is large, uneconomical to be.
[114]
[115]
On the other hand, the step of the immersion is from 1 to 60 seconds at room temperature, preferably 5 to 20 seconds, for example, as being performed for about 10 seconds, and thus a sufficient washing with water for a short time at room temperature when using the washing composition of the invention possible, and there is a yellowing of the steel sheet can be prevented.
[116]
[117]
Further, the washing method of the present invention may further comprise the step of drying, wherein the drying method may be performed by methods such as, not particularly limited, for example a hot-air drying and oven drying.
[118]
[119]
The washing composition of the steel sheet by washing with water as described above can suppress the yellowing of the surface. More preferably, it is possible to further improve the yellowing effect within the water washing by using each of the washing composition with respect to the high-strength steel containing a large amount of Mn. In particular, it is more effective to apply to the high-strength steel sheet containing Mn. Mn of the steel components of said steel sheet is more preferably applied to a steel sheet containing at least 1.0% by weight.
[120]
[121]
The content of Mn steel sheet containing less than 1.0% by weight and there is included within the yellowing performance after pickling, it is less severe yellowing. Accordingly, such steel does the yellowing problem caused by large, it is not necessary to carry out a separate process in yellowing. However, Mn is the quality of the steel sheet and the yellowing occurs after pickling, the this yellowing occurs steel sheet phosphate treatability in a subsequent step after the pickling, and Ni flash (flash) treatability, coatability containing more than 1.0% by weight my yellowing process is necessary since the lowered.
[122]
[123]
The use of the washing composition provided by the present invention, processing within the steel sheet is yellow as a component other than the steel components on the surface of the steel sheet, and a P, C, and O.
[124]
[125]
The P and C is to the oxidation inhibiting component contained in the washing composition in the process of washing with water after pickling of steel sheets remain in the steel sheet surface after drying. On the other hand, O is an element detected from the inevitably formed oxide component to the oxidation inhibiting component and the surface of the steel sheet contained in the above and washing in water washing step after the pickling.
[126]
[127]
After such a P, C, and O is washed with water on the surface of the steel sheet a predetermined amount of the steel plate attached when washing with water and washing with water in which after it is possible to inhibit the re-oxidation in the drying process. Attached to the acid pickling and water washing in yellowing surface-treated steel sheet of the present invention, P is preferably attached in an amount of 0.01 to 5㎎ / ㎡. If the amount of deposition of P 0.01㎎ / ㎡ less can not exhibit sufficient naehwang modified, if P is greater than the adhesion amount 5㎎ / ㎡ has a problem that unevenness occurs in the steel sheet, and the surface is rather dark.
[128]
[129]
In yellowing treated steel sheet of the present invention it is preferably attached to the C content of 0.01 to 500㎎ / ㎡ on the surface of the steel sheet with the P. If the adhesion amount of the C 0.01㎎ / ㎡ is less than if it exceeds can not exhibit a sufficient naehwang modified, 500㎎ / ㎡ has a problem that the phosphate treatability of the surface appearance after the lowering step decreases.
[130]
[131]
Furthermore, in yellow-treated steel sheet of the present invention includes an O together with the P and C, the O is preferably attached in an amount of 0.1 to 500㎎ / ㎡. If the adhesion amount of the O 0.1㎎ / ㎡ less than is the case that there is a problem that can not exhibit a sufficient naehwang modified, exceeds 500㎎ / ㎡ is poor in severe yellowing of the surface appearance, and, after the lowering process, the phosphate treatability there is a problem that.
[132]
[133]
In addition, within the yellowing-treated steel sheet of the present invention, in addition to the exception of the steel components on the surface of the steel sheet, and P, C and O, N, F, Na, Al, Si, S, K, Ca, Ti, V, Cr, Mn , Co, Ni, Cu, Cl, Zn, Zr. The Mo addition may further include. These components may be included in two or more may, of course, be included 1 species thereof.
[134]
[135]
In this case, the components are preferably the total adhesion amount is present in an amount of 0.01 to 5㎎ / ㎡. When the total adhesion amount of the additional component 0.01㎎ / ㎡ is less than the surface appearance and due to this meaningless note the effect of suppressing the fine unevenness occurs on the surface, the adhesion amount is rather increased if it exceeds the staining caused 5㎎ / ㎡ there is a problem dropping.
[136]
[137]
The anti-yellowing treatment, according to an embodiment of the invention steel sheet is a pickling and washing with water the surface of the steel sheet P, C and O, a predetermined amount attached as described above being but can suppress the yellowing of the pickling and washing the steel sheet, in yellow-treated steel sheet the quality is a value measured by a color difference meter (Minolta Spectrophotometer, CM3700d), less than 4.0, the yellowness of the steel sheet surface, is not less than the whiteness of 55. One or more yellow the surface of the steel sheet also exhibit a low value of less than 4.0, the surface appearance is excellent, when the yellowness index is more than 4.0, there is a problem of poor surface appearance, after the step of lowering the phosphate treatability.
[138]
[139]
On the other hand, the surface brightness of the anti-yellowing treatment steel sheet is preferably at least 55. The degree of whiteness is more than 55 exhibit a high value is improved naehwang modified surface appearance is a solid, there is a problem that the brightness of the phosphate treatability after lowering process has a poor surface appearance when less than 55.
[140]
[141]
In yellowing treated steel sheet according to one embodiment of the present invention as described above can effectively inhibit the yellowing occurs due to the property furnace of a steel sheet after pickling, water washing and drying and subsequent hot-rolled steel pickling process in which the steel sheet, hot-rolled steel pickling ointment step, the hot-rolled whether pickling plating process, any process that conduct pickling the steel sheet, such as a continuous annealing process, the stainless steel process, melt coating process, electro-galvanizing process can be produced.
[142]
[143]
In yellowing treated steel sheet as described above it can be produced by washing a steel sheet by applying the pickling oxidation inhibitor composition which can provide the same coating weight on the steel sheet surface P, C, and O as above, and dried.
[144]
[145]
In this case, the oxidation inhibitor composition, for example, if containing a component that can be attached to the P, C, and O on the surface of the steel sheet is not specifically limited. For example, there may be mentioned phosphoric acid ester compound, an amine-based compound, a carbonate compound, a glycol compound, oxidation inhibitor composition comprising the compound, such as acetate.
[146]
[147]
The oxidation inhibitor added to the composition as described above and washing for washing the pickling steel sheet by performing a water washing step of pickling the steel sheet, and can be prepared within the yellowing-treated steel sheet and dried. At this time, by making the residual P, C and O, as described above in a predetermined amount on the surface of the steel sheet can be obtained within the yellowing-treated steel sheet provided by the present invention.
[148]
[149]
At this time, the content of the P, C, and O is attached to the surface of the steel sheet can be obtained by appropriately adjusting the composition in the acid or tax and washing. In addition, it is possible to obtain by controlling the time for adjusting the interval for performing the pickling after the water washing step, or washing with water. Thus, so long as the content as described above can be attached to the P, C, and O, the method is not particularly limited.
[150]
Mode for the Invention
[151]
Hereinafter, the present invention will be described in more detail through specific examples. The following examples are for exemplary purposes only and for a better understanding of the present invention, but the scope of the present invention is not limited thereto.
[152]
[153]
Example
[154]
Experimental Example 1: in accordance with the composition of the washing composition yellowing evaluation prevention effect
[155]
Pickling the material was used by processing into a size of 100 × 100㎟ the hot rolled steel sheet of thickness of 1.2mm 980MPa grade manganese 2.8% by weight and silicon 1.1% by weight width × length 30 seconds in 500ml of hydrochloric acid of 15 weight% and 80 ℃ deposition was carried out by pickling.
[156]
[157]
On the other hand, as a result of washing with water the pickling steel sheet obtained was carried out by the addition of 0.5% by weight of the washing composition of this invention in distilled water at ambient temperature 500ml immersed for 10 seconds.
[158]
[159]
At this time, the washing composition is used to obtain an end washing composition was prepared in the ingredients and contents as described in Table 1 below. To the basis of 100% by weight in Table 1 as the remaining amount is included with water.
[160]
[161]
On the other hand, to the respective water washing In such compositions measured yellowing room intelligence and solution stability of the steel sheet are shown in Table 1.
[162]
[163]
At this time, the yellow room intelligence by measuring the yellow color of the samples undergo a finishing pickling using a color difference meter (Minolta Spectrophotometer, CM3700d) was evaluated by the following standard.

Claims

[Claim 1]6 to 14% by weight of phosphoric acid ester compound, an amine-based compound of 6 to 19% by weight, sodium carbonate, 1 to 9% by weight of ammonium acetate, 1 to 9% by weight, EDTA (ethylenediaminetetraacetic acid), 1 to 14% by weight and the balance washing with water the composition of pickling the steel sheet containing water.
[Claim 2]
A phosphoric acid ester compound 15 to 24% by weight, of citric acid of 5 to 15% by weight, sodium carbonate, 2 to 10% by weight, sodium acetate from 2 to 7% by weight, DTPA (diethylene tetramine pentaacetic acid) 1 to 7% by weight and the balance water washing with water the composition of pickling the steel sheet comprising a.
[Claim 3]
According to claim 1 or 2, wherein the phosphoric acid ester compound is a bisphenol A- bis (diphenyl phosphate), triaryl phosphate, isopropyl, dimethyl methyl phosphate, tetraphenyl-m- phenylene bis (phosphate), tri-ethyl phosphate and a tree of at least one compound selected from the group consisting of phenyl phosphate, washed with water composition of pickling the steel sheet.
[Claim 4]
The method of claim 1 wherein the amine compound is ethylamine, methylamine, propylamine, butylamine, polyethylene amine, polypropylene amine, polybutyl amines, and poly is at least one compound selected from the group consisting of an arylamine, washing with water the composition of pickling the steel sheet.
[Claim 5]
According to claim 1 or 2 wherein the washing composition comprises a pH of 8.0 or more, a washing composition of pickling the steel sheet.
[Claim 6]
According to claim 1 or 2 wherein the washing composition comprises a pH of 8.5 to 11.5, the water rinsing composition of pickling the steel sheet.
[Claim 7]
According to claim 1 or 2 wherein the washing composition comprises a composition of water washing, pickling the steel sheet to be diluted in water in an amount of 0.05 to 1.5% by weight.
[Claim 8]
A phosphoric acid ester compound of 6 to 14% by weight, the amine-based compound of 6 to 19% by weight, sodium carbonate, 1 to 9% by weight of ammonium acetate, 1 to 9% by weight, EDTA 1 to 14% by weight and the balance pickling the steel sheet by mixing the water part step of preparing a washing composition; The method comprising diluting the composition to the washing water; And a water rinsing method of pickling the steel sheet comprises the step of pickling the steel sheet is immersed in the washing composition.
[Claim 9]
A phosphoric acid ester compound 15 to 24% by weight, of citric acid of 5 to 15% by weight, sodium carbonate, 2 to 10% by weight, sodium acetate from 2 to 7% by weight, DTPA (diethylene tetramine pentaacetic acid) 1 to 7% by weight and the balance water the step of mixing to prepare a water washing composition of pickling the steel sheet; The method comprising diluting the composition to the washing water; And a water rinsing method of pickling the steel sheet comprises the step of pickling the steel sheet is immersed in the washing composition.
[Claim 10]
Claim 8 according to any one of claims 9, further comprising: diluting the composition to the washing water, flushing methods, pickling the steel sheet is carried out by dilution in water, the washing composition in an amount of 0.05 to 1.5% by weight.
[Claim 11]
Claim 8 or claim 9, wherein the phosphoric acid ester compound is a bisphenol A- bis (diphenyl phosphate), triaryl phosphate, isopropyl, dimethyl methyl phosphate, tetraphenyl-m- phenylene bis (phosphate), tri-ethyl phosphate and triphenyl phosphate 1 water washing method of, pickling the steel sheet at least one compound selected from the group consisting of.
[Claim 12]
The method of claim 8, wherein the amine compound is ethylamine, methylamine, propylamine, butylamine, polyethylene amine, polypropylene amine, polybutyl amines, and poly is at least one compound selected from the group consisting of an arylamine, washing method of pickling the steel sheet.
[Claim 13]
Claim 8 or claim 9, wherein the washing with water of the composition is washed with water, pickling the steel sheet a pH of 8.0 or more.
[Claim 14]
A steel sheet containing Mn more than 1.0 wt%, the pickling, and as a component other than the steel components on the surface of the steel sheet after the washing with water 0.01 ~ 5㎎ / ㎡ of P, 0.01 ~ 500㎎ / ㎡ of C and 0.1 ~ 500㎎ / ㎡ the O contained within the yellowing-treated steel sheet for.
[Claim 15]
15. The method of claim 14, wherein the steel sheet has a yellowness index less than 4.0 and a whiteness of 55 or more within the yellowing-treated steel sheet.
[Claim 16]
15. The method of claim 14, with the exception of the steel components to the surface of the steel sheet N, F, Na, Al, Si, S, K, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Cl, Zn, Zr and at least one component 0.01 ~ 5㎎ / ㎡ further contains within the yellowing-treated steel sheet which is to be selected from the group consisting of Mo.
[Claim 17]
Claim 14 to 16 according to any one of claims, wherein the steel sheet is Ni flash plating or Ni plating or Zn flash in yellow-treated steel sheet which comprises a Zn plating layer by.
[Claim 18]
Of claim 14 to claim 16 according to any one of, wherein the steel sheet is within the yellow-treated steel sheet comprising a phosphate-treated layer according to the phosphating solution.
[Claim 19]
Of claim 14 to claim 16 according to any one of, wherein the steel sheet is Zn, Al, hot dipping, or is within the yellow-treated steel sheet comprising a plated layer by electroplating and at least one component of the Mg and Si.
[Claim 20]
Of claim 14 to claim 16 according to any one of, wherein the steel sheet is within the yellow-treated steel sheet comprises a resin layer of the resin composition is applied.
[Claim 21]
Of claim 14 to claim 16 according to any one of, wherein the steel sheet is within the yellow-treated steel sheet would the rust preventive oil is applied.