JP2016138331A - Anode aluminum dye leveling-retarding assistant, treatment liquid therefor, and anode aluminum dye leveling-retarding treatment process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide dyeing finishing of thin color free from a color difference while making the excellent mechanical properties and chemical properties of an anodic oxide film consistent, having a satisfactory dye leveling-retarding effect, preventing the local color difference or surface unevenness produced in the dyeing step of anodized aluminum.SOLUTION: Provided are an anode aluminum dye leveling-retarding assistant containing an auxiliary additive comprising: the first active component including one or more kinds selected from carboxylic acid group-containing compounds, carboxylates, substituted carboxylates, carboxylic acid anhydrides, amino acid salts and amino acid anhydrides; the second active component including sulfonic acid group-containing compounds and/or sulfonates; pH stabilizers; blocking preventives; and scale preventives, a treatment liquid for the anode aluminum dye leveling-retarding assistant using the assistant, and an anode aluminum dye leveling-retarding treatment process.SELECTED DRAWING: None

Description

  The present invention relates to an anodic aluminum level dyeing process, and more particularly to an anodic aluminum level dyeing / dyeing assistant and a treatment liquid thereof, and an anodic aluminum level dyeing / dyeing process.

  Anodized aluminum is light and high in hardness, has excellent wear resistance and corrosion resistance, etc. In addition, in order to obtain an excellent decorative function, the surface of the aluminum material is dyed and colored after oxidation treatment of the anode. Can be given various appearances. Thus, anodized aluminum is currently one of the most widely used substrates for electrical products such as smartphones and tablets.

  The phenomenon of poor dyeing is common during production. In the entire oxidation dyeing process of the aluminum material, the defective dyeing is related not only to the oxidation process but also to the dyeing pretreatment process whose cause is unstable. Since the anodized aluminum product has an aluminum oxide film rich in micropores on the surface, strong acid in the anodizing tank tends to remain in these micropores. Residual strong acid adversely affects the subsequent dyeing process. First, the remaining strong acid dissolves in the solution in the dye tank, so that the pH value of the dye solution is changed, and the dye is discolored and decolored. Next, since the remaining strong acid occupies a part of the micropores on the oxide film surface, the adsorption of the dye molecules to the oxide film surface becomes uneven, causing local color difference or surface unevenness. Such a problem can be avoided if an appropriate treatment is performed on the surface of the anode aluminum before dyeing.

  Moreover, when actually used, it may be necessary to manufacture the work with a relatively light color and no color difference. According to the adsorption principle, the conventional method of adjusting the anodizing or dyeing process flow to achieve such a color effect during actual production causes several defects. For example, by reducing the anodic oxidation film thickness by shortening the anodic oxidation time, and further achieving the effect of suppressing the adsorption of the dye, or by reducing the dye concentration in the dye tank, or shortening the dyeing time Thus, there is a method of suppressing the adsorption of the dye to the oxide film and further achieving the effect of a light-colored dyeing finish. However, thinned anodized aluminum products have properties such as hardness, wear resistance, and corrosion resistance that decrease with their changes. Also, if the dye concentration is too low, fluctuations in the concentration of the dye in the bath liquor will be large, making it difficult to control the production line, and significantly increasing the color difference between products in different batches. On the other hand, if the dyeing time is too short, the coloring will be fast, causing uneven dyeing and color differences between products in different batches.

  Therefore, there is a strong expectation of a pre-dyeing prescription and process that enables smooth dyeing finish processing of light colors on the premise that the anodic aluminum oxidation process and dyeing process are not basically changed during the anodization process. Yes.

  In view of the above circumstances, the present invention prevents local color differences or surface unevenness caused by anodized aluminum in the dyeing process in the prior art, and has no color difference while achieving both excellent mechanical characteristics and chemical characteristics of the anodized film. In order to solve the problem that it is difficult to realize a light-colored dyeing finish process smoothly, an anode aluminum level dyeing / dyeing aid is provided.

  In the first aspect, the present invention includes a carboxylic acid group-containing compound, a carboxylic acid salt, a substituted carboxylic acid salt, a carboxylic acid anhydride, an amino acid salt, and one or more kinds selected from amino acid anhydrides. 1 type of active ingredient, 2nd active ingredient containing a sulfonic-acid-group containing compound and / or sulfonate, 1 type, or 2 or more types chosen from a pH stabilizer, an antiblocking agent, and a scale inhibitor An anodic aluminum leveling / dyeing aid comprising an auxiliary additive is provided.

  The first active ingredient has an effect of slowing dyeing when the anodic oxide film is dyed. In this way, the thickness of the anodic aluminum oxide film (if the anodic aluminum film is too thin, the mechanical strength of the product tends to be insufficient) or the dyeing time (if the dyeing time is too short, the dyeing is uneven) There is no need to reduce

  Preferably, the carboxylic acid group-containing compound includes a carboxylic acid and / or a substituted carboxylic acid.

  The carboxylic acid includes tricarboxylic acid, dicarboxylic acid, and monocarboxylic acid. Here, the effect of gradually dyeing the tricarboxylic acid, dicarboxylic acid, and monocarboxylic acid is weakened in this order.

  Preferably, the substituted carboxylic acid comprises an amino acid, a hydroxy acid, a halogenated acid, and / or a carbonyl acid.

  Preferably, the amino acid is selected from glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, aspartic acid, histidine, asparagine, glutamic acid, lysine, glutamine, methionine, arginine, serine, threonine, cysteine, and proline. 1 type or 2 types or more included.

  Preferably, the carboxylic acid group-containing compound is acetic acid, glycolic acid, propionic acid, acrylic acid, formic acid acetic anhydride, tartaric acid (2,3-dihydroxybutanedioic acid), malic acid (2-hydroxybutanedioic acid). ), Malonic acid (propanedioic acid), lactic acid (hydroxypropanoic acid), crotonic acid (2-butenoic acid), maleic acid (cis-butenedioic acid), oxaloacetic acid, succinic acid (1,2-butanedioic acid) 1,3-glutaric acid, α-ketoglutaric acid, 1-hexanoic acid, 1,4-adipic acid, citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid), heptanoic acid, 1,5- Pimelic acid, benzoic acid, 1,2-phthalic acid, 1,3-phthalic acid, 1,4-phthalic acid, salicylic acid (2-hydroxybenzoic acid), and monocarboxylic acid polymer or polycarboxylic acid Comprising one or more selected from a polymer.

  Preferably, the carboxylate salt includes a carboxylic acid sodium salt, potassium salt, magnesium salt, or calcium salt, and the substituted carboxylate salt includes a substituted carboxylic acid sodium salt, potassium salt, magnesium salt, or calcium salt. The amino acid salt includes an amino acid sodium salt, potassium salt, magnesium salt, or calcium salt.

  The second active ingredient contributes to the removal of the acid remaining on the surface of the anodic aluminum product, prevents the strong acid in the anodizing tank from mixing into the dye tank, and contributes to leveling. It is possible to improve once and impart an appropriate acidity.

  Preferably, the sulfonic acid group-containing compound is one or more selected from methylsulfonic acid, sulfamic acid, benzenesulfonic acid, p-toluenesulfonic acid, taurine, mercaptopropanesulfonic acid, and trifluoromethanesulfonic acid. including.

  Preferably, the sulfonate includes a sulfonate sodium salt, potassium salt, magnesium salt, or calcium salt.

  Depending on the first active ingredient, the second active ingredient, and the auxiliary additives, the anodic aluminum leveling / dyeing aid according to the present invention may be a powder preparation or a liquid preparation.

  Further, the anode aluminum level dyeing / slow dyeing assistant contains water. That is, a processing liquid is obtained by mixing a powder formulation or a liquid formulation with water to form a mixed system. In the mixed system, the concentration of the first active ingredient is 0.01 g / L to 200 g / L, and the concentration of the second active ingredient is 0.5 g / L to 400 g / L. The concentration of the agent is 0.5 g / L to 400 g / L.

  Preferably, in the mixed system, the concentration of the first active ingredient is 0.5 g / L to 50 g / L, and the concentration of the second active ingredient is 5 g / L to 100 g / L. The concentration of the additive is 5 g / L to 100 g / L.

  The anodic aluminum level dyeing / loosening aid according to the first aspect of the present invention is a good level dyeing / dyeing dye due to a synergistic effect between the first active ingredient, the second active ingredient, and the auxiliary additive. The effect is obtained, reducing the color difference between products in different batches while maintaining the good mechanical strength of the anodic aluminum oxide film, without the need to reduce the anodic aluminum film thickness, dye concentration, or dyeing time, Furthermore, a uniform dyeing effect can be achieved.

  In a second aspect, the present invention provides a treatment solution for an anode aluminum level dyeing / dyeing assistant obtained by adding the anode aluminum level dyeing / dyeing assistant according to the first aspect of the present invention to water and mixing them uniformly. I will provide a.

  Preferably, in the treatment liquid, the concentration of the first active ingredient is 0.01 g / L to 200 g / L, and the concentration of the second active ingredient is 0.5 g / L to 400 g / L, The concentration of the auxiliary additive is 0.5 g / L to 400 g / L.

  More preferably, in the treatment liquid, the concentration of the first active ingredient is 0.5 g / L to 50 g / L, the concentration of the second active ingredient is 5 g / L to 100 g / L, The concentration of the auxiliary additive is 5 g / L to 100 g / L.

  More preferably, in the treatment liquid, the concentration of the first active ingredient is 6 g / L, the concentration of the second active ingredient is 27 g / L, and the concentration of the auxiliary additive is 27 g / L. is there.

  In the third aspect, the present invention is such that the anodized anodic aluminum is added to the treatment liquid for the anodic aluminum leveling / dyeing assistant according to the second aspect of the present invention, and the anodic aluminum is treated at 5 to 90 ° C. Provided is an anode aluminum level dyeing / dyeing treatment process including a step of removing from a treatment liquid and washing after treating for 60 minutes to 60 minutes, and a step of dyeing and sealing the washed anode aluminum.

  Specifically, the process of treating the anodic aluminum with the treatment solution for the anodic aluminum level dyeing / loosening aid is preferably performed at 20 ° C. to 50 ° C. for 3 to 8 minutes, and preferably at 25 ° C. for 5 minutes. It is more preferable.

  Preferably, the treatment liquid of the anode aluminum level dyeing / loosening aid is adjusted to a pH of 0.5 to 7.0, more preferably to a pH of 0.5 to 4.0, and even more preferably. The pH is adjusted to 2.0 to 2.5.

  The anodic aluminum product has a dyeing activity of less than 100% after being treated with the anodic aluminum leveling / dyeing aid according to the present invention, indicating that it has a slow dyeing effect. The formula for calculating the staining activity is shown below.

Formula 1

  The following (1) to (5) are carried out by performing dyeing preliminary treatment on the anodized aluminum material by the anodic aluminum leveling / dyeing assistant and the leveling / slowening process using the same. ) Has a beneficial effect as shown in.

  (1) The leveling and slow dyeing effect imparted to the surface of the aluminum product makes it easy to control the anodic aluminum dyeing process, that is, the following effects (1-1) to (1-3) are brought about.

  (1-1) Such dyeing pretreatment has the greatest advantage that there is no need to change the process flow of anodizing or dyeing, and in this way, it is limited to the thickness of the aluminum anodized film during product design. Therefore, there is no need to worry about the influence of the aluminum anodized film thickness on the dyeing uniformity when dyeing thereafter. Due to this advantage, the anodic aluminum level dyeing / loosening aid is used when the product is dyed in a uniform light color and the oxide film needs to be formed to a thickness to maintain sufficient mechanical properties. Is particularly useful.

  (1-2) When the preliminary treatment is performed using the anode aluminum level dyeing / loosening aid according to the present invention in the production line, the color difference between the products of different batches obtained is reduced.

  (1-3) During the process of anodization, a difference in anodized film thickness is often caused on the surface of an aluminum product due to non-uniform current density distribution. If the color difference that occurs during dyeing due to the difference in the anodic oxide film thickness is too large, surface unevenness occurs. However, the dyeing finish processing using the anodic aluminum leveling and slow dyeing assistant according to the present invention can solve this problem satisfactorily. .

  (2) When the preliminary dyeing treatment is performed on the anodized aluminum material by the composition and process of the anodic aluminum leveling and dyeing assistant according to the present invention, the sealing treatment is not affected thereafter.

  (3) The degree of fading due to sunlight irradiation of the anodic aluminum product treated by the anodic aluminum level dyeing / dyeing process according to the present invention was not significantly different from that of the non-treated anodic aluminum product.

  (4) Since the anode aluminum level dyeing / dyeing process according to the present invention is easily applied to the conventional production line, it is necessary to produce anode aluminum that needs to be dyed lightly and maintain a certain oxide film thickness. Is particularly useful.

  (5) The composition of the anodic aluminum leveling / dyeing assistant according to the present invention is not limited to the type of aluminum material, and can be applied to various types of aluminum materials. Also gentle.

  A significant effect of the embodiment of the present invention will be described below. These effects are obvious from the description of the specification and the like or are known by carrying out the embodiments of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, if it is assumed that the idea of the present invention is not departed from, the person skilled in the art belongs to the protection scope of the present invention even if a plurality of modifications and changes are made. Should be understood to be.

  The following examples further illustrate embodiments of the present invention. The present invention is not limited to the following specific examples. The present invention can be implemented with appropriate modifications without departing from the scope of protection of the claims of the present invention.

  In addition, all the aluminum sheets used for the following Example of this invention are 50 mm x 30 mm (length x width) in size.

  All the dyes used in the following examples of the present invention are manufactured by Okuno Pharmaceutical Co., Ltd., and are not limited to the products of the company.

  All the anodic oxidation according to the following embodiments of the present invention is performed by the following process, and it is natural that the anodic oxidation process is not limited to the following processes when the present invention is carried out.

Aluminum sheet → cleaning → smut removal → anodic oxidation Cleaning process: “Ram Clean 105 (product number)”, 50 g / L, 60 ° C. cleaning for 5 minutes.

  Smut removal process: “Ram DSM30 (product number)”, 50 mL / L, room temperature for 30 seconds.

Anodizing process: “98% H ₂ SO ₄ ”, 220 g / L, 18 ° C., voltage 14 V, oxidation time 10 minutes to 30 minutes (oxide film thickness 5 μm to 20 μm).

<Example 1>
The method for preparing the anode aluminum level dyeing / loosening aid is shown below.

  100 g of sodium citrate, 450 g of sulfamic acid, and 450 g of a pH stabilizer were uniformly mixed to prepare 1 kg of a powder preparation of an anode aluminum leveling / slow dyeing assistant.

<Example 2>
The method for preparing the treatment solution for the anodic aluminum level dyeing / loosening aid is shown below.

  The powder preparation of the anodic aluminum leveling / dyeing aid prepared in Example 1 above was added to deionized water and the concentrations were 0.5 g / L, 1.5 g / L, 3 g / L, and 6 g / L, respectively ( A processing solution for an anodic aluminum leveling / slow dyeing assistant, which is based on the concentration of sodium citrate, the first active ingredient, was prepared.

<Example 3>
The anode aluminum level dyeing / dyeing process includes the following steps (1) to (3).

  (1) Four anodized aluminum test pieces having a model number of 5052 were anodized and washed with water, and then treated with anodic aluminum level dyeing / dyeing assistants prepared in Example 2 of the present invention ( (25 ° C.) for 5 minutes, and then removed from the treatment solution and washed with deionized water. Here, the anodic oxidation time of the aluminum test piece is 20 minutes, and the oxide film thickness is about 15 μm.

  (2) Subsequently, the aluminum sheet treated with the treatment solution of the anodic aluminum level dyeing / loosening aid of different concentrations was put into the dyeing solution and dyed for 5 minutes, and then the aluminum sheet was taken out and washed. Here, the dye used is a black dye “TAC Black SLH415AN” manufactured by Okuno Pharmaceutical Co., Ltd., and has a concentration of 10 g / L. The temperature of the dye tank is adjusted to 25 ° C.

  (3) Finally, the washed aluminum sheet was dyed and sealed.

  Investigate leveling effect and slow dyeing effect with processing solution of anode aluminum leveling / dyeing assistant prepared at different concentrations (same operating conditions such as pH, processing time, temperature, etc. using the same dye) Therefore, the color tone Lab value at the center position of the aluminum sheet dyed in step (2) of Example 3 was measured. The difference ΔE calculated by comparing the Lab value of the sample treated with the level dyeing / loosening aid at each concentration with the Lab value of the blank sample indicates the difference in color shade between the samples. The formula for calculating the ΔE value is shown below.

Formula 2

_Wherein, L _1, a 1, _{b 1} are respectively L empty sample, a, b values _indicate L _i, a i, _{b i} is the sample respectively L, a, b values.

  Thereafter, the staining activity was measured. The dyeing activity indicates the hue of the dyed anode aluminum test piece, and the larger the value, the darker the hue. The magnitude of the dyeing activity value can also be used to determine whether pre-dyeing with a leveling / slow dyeing aid effectively slows down the dyeing speed.

  The method for measuring the staining activity is shown below.

  After adding 50 mL of NaOH having a concentration of 50 g / L to the beaker and heating to 50 ° C., a dyed test piece was put and the film was removed. After the film was completely removed, the test piece was taken out with pliers. The liquid attached to the test piece, pliers, and thermometer was washed with ion-exchanged water and collected in a beaker. After leaving the beaker for 10 minutes at a constant temperature (50 ° C.) while stirring. Then, it was cooled to 25 ° C. within 5 minutes, transferred to a 100 mL volumetric flask to make a constant volume, allowed to stand for 30 minutes, and then the absorbance (wavelength: about 568 nm) was measured within 2 hours.

  The measurement results of the experiment are shown in Table 1. A sample in which the concentration of the level dyeing / loosening aid in Table 1 is 0 g / L is defined as an empty sample. The empty sample was an anodic aluminum sample in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution. After dyeing, the color difference, activity, etc. were measured.

  According to the results in Table 1, the difference ΔE between the sample pre-dyed with the anodic aluminum level dyeing / dyeing assistant having a concentration of 0.5 g / L to 6 g / L increases with the increase in concentration, It can be seen that a clear dyeing effect is exhibited by pretreatment with a leveling / dyeing assistant under the same dyeing conditions. Similar conclusions were confirmed by the measurement results of staining activity. That is, the sample not pre-treated with the level dyeing / loosening aid has the highest activity because the dyed color is the darkest, while the color of the dyed sample becomes lighter as the level of the leveling / dyeing aid increases, The activity is also reduced. However, when the level of the leveling / dyeing assistant is 3 g / L to 6 g / L, the tendency to lighten the color becomes weaker. Is shown.

<Example 4>
In this example, the effect of leveling and slow dyeing was investigated when the first active component in the composition of the anode aluminum level dyeing and slowing aid was a single organic carboxylic acid of a different type.

  The method for preparing the treatment solution for the anodic aluminum level dyeing / loosening aid is shown below.

  100 g of citric acid, 450 g of sulfamic acid, and 450 g of a pH stabilizer were uniformly mixed to prepare 1 kg of a powder preparation of an anode aluminum leveling / slow dyeing assistant. Thereafter, the resulting powder formulation is added to deionized water to prepare a treatment solution for an anode aluminum level dyeing / loosening aid having a concentration of 6 g / L (based on the concentration of citric acid as the first active ingredient). did.

  Each of malic acid, tartaric acid, crotonic acid and lactic acid is used as the first active ingredient, and in the same manner as described above, the first active ingredient is malic acid, tartaric acid, crotonic acid and lactic acid, respectively, and the concentration is 6 g / L (first A processing solution of an anodic aluminum level dyeing / loosening aid, which is based on the concentration of one active ingredient), was prepared.

  In the treatment liquid of anode aluminum level dyeing / loosening aid using malic acid, tartaric acid, crotonic acid, and lactic acid prepared in this example as the first active components, the same operating conditions as above (at 25 ° C. for 5 minutes) In an immersion), after pre-dyeing the anode aluminum test piece (aluminum material model No. 5052), the black dye “TAC Black SLH415AN” having a concentration of 10 g / L was used under the same conditions as described above (55 ° C.). Stained for 15 minutes. The color tone Lab value of the finished product was measured. The oxide film thickness of the anode aluminum test piece used in this example is about 15 μm. The experimental results are shown in Table 2. “Blank” in Table 2 refers to an empty sample. The empty sample was an anodic aluminum sample in which other experimental processes were carried out in the same manner other than being immersed in the soaking / slow dyeing assistant solution, and after the dyeing, the color difference and the like were measured.

  According to the results in Table 2, it is shown that all of the five types of organic carboxylic acids measured in this example have a slow dyeing effect. Further, after different organic carboxylic acids are added to the level dyeing / loosening aid at the same concentration and dyed, a different ΔE is obtained as compared with the color tone of the empty sample. The larger the ΔE, the greater the difference in color shade. The experimental results show that the slow dyeing effect of carboxylic acid is clearly different depending on the type of carboxylic acid. Among them, the sample dyed with the composition containing citric acid as the first active ingredient has the lightest color, and the color difference ΔE between the measured Lab value and the empty sample is the largest. It becomes strong and weakens in the order of citric acid, tartaric acid, malic acid, crotonic acid, and lactic acid. That is, the effect of slow dyeing of tricarboxylic acid, dicarboxylic acid and monocarboxylic acid becomes weaker in this order.

<Example 5>
In this example, the effect of leveling and slow dyeing was investigated when the first active component in the composition of the anode aluminum level dyeing and dyeing assistant was a two-component mixture.

  The method for preparing the treatment solution for the anodic aluminum level dyeing / loosening aid is shown below.

  A total mass of 100 g of citric acid and tartaric acid was uniformly mixed with citric acid: tartaric acid = 100: 0, 70:30, 30:70, 0: 100 mass ratio with 450 g of sulfamic acid and 450 g of pH stabilizer, respectively. A powder formulation of an aluminum level dyeing / loosening aid was prepared. Thereafter, the resulting powder formulations are each added to deionized water, and citric acid, citric acid: tartaric acid (70:30), citric acid: tartaric acid (30:70), and tartaric acid are the first active ingredients, respectively, and the concentration is 6 g. A treatment solution of an anode aluminum level dyeing / loosening aid that was / L (based on the concentration of the first active ingredient) was prepared.

  In this example, an anode aluminum level dyeing / loosening aid processing solution to which citric acid and tartaric acid were added in different ratios, and an anode aluminum test piece (aluminum material) under the same operating conditions as above (soaked at 25 ° C. for 5 minutes) After performing dyeing pretreatment (namely, dyeing finishing process) on the model No. 5052), it was dyed with a black dye “TAC Black SLH415AN” having a concentration of 10 g / L for 5 minutes under the same conditions (55 ° C.). The color tone Lab value and dyeing activity of the finished product were measured. The empty sample of this example is an anode aluminum test piece (aluminum material model No. 5052) that is not pre-stained with a black dye “TAC Black SLH415AN” having a concentration of 10 g / L for 5 minutes under the same conditions as described above (55 ° C.). It was obtained by direct staining. The color tone Lab value and staining activity of the empty sample were measured. The oxide film thickness of the anode aluminum test piece used in this example is about 15 μm. The experimental results are shown in Table 3.

  According to the results of Table 3, when two types of organic carboxylic acids (citric acid and tartaric acid) are added as active ingredients, the slow dyeing efficiency shows a linear relationship with the concentration of the organic carboxylic acid. Further, when the proportion of citric acid is relatively high, ΔE for the empty sample is larger and the activity is lower, indicating that the slow dyeing effect is relatively strong. This conclusion is similar to the result of Example 4.

<Example 6>
In this example, when the second active ingredient in the composition of the anodic aluminum level dyeing / loosening aid is a different compound, or the ratio of the first active ingredient, the second active ingredient and the auxiliary additive is different. The leveling and slow dyeing effects were investigated.

  The method for preparing the treatment solution for the anodic aluminum level dyeing / loosening aid is shown below.

  Composition A: Sodium citrate having a total mass of 100 g was uniformly mixed with 450 g of sulfamic acid and 450 g of a pH stabilizer to prepare a powder formulation of an anode aluminum leveling / dyeing aid. Thereafter, the resulting powder formulation was added to deionized water to prepare a treatment solution for an anode aluminum level dyeing / dyeing assistant having a concentration of 6 g / L (based on the concentration of the first active ingredient).

  Composition B: Sodium citrate having a total mass of 100 g was uniformly mixed with 450 g of sodium benzenesulfonate and 450 g of a pH stabilizer to prepare a powder formulation of an anode aluminum level dyeing / loosening aid. Thereafter, the resulting powder formulation was added to deionized water to prepare a treatment solution for an anode aluminum level dyeing / dyeing assistant having a concentration of 6 g / L (based on the concentration of the first active ingredient).

  Composition C: Sodium citrate having a total mass of 100 g was uniformly mixed with 550 g of sulfamic acid and 350 g of a pH stabilizer to prepare a powder preparation of an anode aluminum level dyeing / loosening aid. Thereafter, the resulting powder formulation was added to deionized water to prepare a treatment solution for an anode aluminum level dyeing / dyeing assistant having a concentration of 6 g / L (based on the concentration of the first active ingredient).

  The pH of the treatment liquid of the leveling / slow dyeing assistant prepared with the above compositions A to C is about 2.0.

  A processing solution of the anodic aluminum leveling / dyeing assistant of composition A to composition C prepared in this example, and anodic aluminum test piece (aluminum material model number) under the same operating conditions as above (immerse for 5 minutes at 25 ° C.) 5052) was subjected to dyeing pretreatment (ie, dyeing finishing), and then dyed with a black dye “TAC Black SLH415AN” having a concentration of 10 g / L for 5 minutes under the same conditions (55 ° C.) as described above. The color tone Lab value and dyeing activity of the finished product were measured. The empty sample of this example is an anode aluminum test piece (aluminum material model No. 5052) which is not pre-stained with a black dye “TAC Black SLH415AN” having a concentration of 10 g / L under the same conditions as described above (25 ° C., 5 minutes). And obtained by direct dyeing. The color tone Lab value and staining activity of the empty sample were measured. The oxide film thickness of the anodic aluminum test piece used in this example is about 18 μm. The experimental results are shown in Table 4.

  According to the results in Table 4, the use of a different second active ingredient has a certain influence on the dyeing effect. Composition A has a relatively large ΔE and lower activity, indicating that sulfamic acid has a mild dyeing effect superior to sodium benzenesulfonate. On the other hand, when the second active ingredient is sulfamic acid, even if the addition amount is finely adjusted, the effect of slow dyeing is not greatly affected.

<Example 7>
In this example, the leveling and slow dyeing effects when the dyeing pretreatment was applied to different types of dyes were investigated.

  The anode aluminum level dyeing / dyeing process includes the following steps (1) to (3).

  (1) Treatment of 4 aluminum test pieces having a model number of 5052 after anodic oxidation and washing with water, respectively, and an anodic aluminum leveling / slow dyeing assistant with a concentration of 6 g / L prepared in Example 2 of the present invention It was immersed in a liquid (25 ° C.) for 5 minutes, then removed from the treatment liquid and washed with deionized water. Here, the anodic oxidation time of the aluminum test piece is 20 minutes, and the oxide film thickness is about 15 μm.

  (2) Subsequently, the treated aluminum sheet was put into a dye tank of red, yellow, blue, and black dyes and dyed for 5 minutes, and then the aluminum sheet was taken out and washed. Here, the dye used is a dye manufactured by Okuno Pharmaceutical Co., Ltd., and has a concentration of 10 g / L. The temperature of the dye tank is adjusted to 25 ° C.

  (3) Finally, the washed aluminum sheet was dyed and sealed.

  At the same time, the test was performed using an aluminum oxide sheet that was not pre-dyed with the treatment solution for the anode aluminum level dyeing / loosening aid of this example as an empty sample.

  The color tone Lab value and staining activity of the dyed finished product were measured. The experimental results are shown in Table 5. “Blank” in Table 5 refers to an empty sample (a total of 4 samples corresponding to different dyes). The empty sample is an anodic aluminum sample in which other experimental processes were carried out in the same manner except that it was not immersed in the level dyeing / loosening aid solution, and it was one of four dyes (red / yellow / blue / black). After dyeing, the color difference, activity, etc. were measured.

  According to the results of Table 5, the composition of the level dyeing / loosening aid has a slow dyeing effect on the dyeing of the anode aluminum test piece with four kinds of dyes. However, when the use concentration of the level dyeing / loosening aid is 6 g / L, the amount of decrease in the activity varies depending on the type of the dye, indicating that the slow dyeing effect varies depending on the color. Among them, since the activity of the black pigment (TAC Black SLH415AN) is the lowest, the slow dyeing effect of the level dyeing / dyeing assistant on the black pigment is most obvious.

<Example 8>
In this example, the influence of dyeing finishing pretreatment performed at different pH depending on the treatment solution of the anode aluminum level dyeing / loosening aid was investigated.

  The powder preparation of the anodic aluminum level dyeing / loosening aid prepared in Example 1 of the present invention becomes a treatment liquid having a concentration of 6 g / L and 15 g / L (based on the concentration of the first active ingredient). Dilute to After adjusting the pH of the diluted processing solution to 1.5 and 2.5, respectively, an aluminum sheet anodized at 25 ° C. (model number 5052, oxide thickness of about 15 μm) was immersed in the processing solution for 5 minutes, Then, it removed from the process liquid and wash | cleaned with deionized water. Subsequently, the aluminum sheet was immersed in a black dye (TAC Black SLH415AN) having a concentration of 10 g / L and dyed under the same conditions as described above (dye at 55 ° C. for 15 minutes). Finally, the color tone Lab value and dyeing activity of the finished product were measured. The experimental results are shown in Table 6. “Blank” in Table 6 refers to an empty sample. The empty sample was an anodic aluminum sample in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution. After dyeing, the color difference, activity, etc. were measured.

  According to the results in Table 6, the pH value of the treatment liquid has a great influence on the staining. When the pH is 1.5, the activity decreases to about 40% to 44% regardless of the concentration of the treatment liquid (6 g / L or 15 g / L). Since all of the treatment liquids at the concentration are reduced in activity to about 26% to 28%, the slow dyeing effect is similar. According to the results, when the pH is relatively high, the slow dyeing effect of the leveling / slow dyeing assistant is more obvious.

<Example 9>
In this example, the influence on the dyeing of the dyeing finishing pretreatment performed on the anode aluminum workpiece with different immersion times depending on the treatment solution of the anode aluminum level dyeing / loosening aid was investigated.

  The powder preparation of the anodic aluminum level dyeing / loosening aid prepared in Example 1 of the present invention was diluted to a treatment liquid having a concentration of 6 g / L (based on the concentration of the first active ingredient). After adjusting the pH of the diluted treatment solution to 2.0, an aluminum sheet (part number 5052, oxide film thickness of about 15 μm) anodized at 45 ° C. is immersed in the treatment solution for 2 minutes, 5 minutes, and 8 minutes, respectively. Then, it was taken out from the treatment liquid and washed with deionized water. Subsequently, the aluminum sheet was immersed in a black dye (TAC Black SLH415AN) having a concentration of 10 g / L and dyed under the same conditions as described above (dye at 55 ° C. for 15 minutes). Finally, the color tone Lab value and dyeing activity of the finished product were measured. The experimental results are shown in Table 7. “Blank” in Table 7 refers to an empty sample. The empty sample was an anodic aluminum sample in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution. After dyeing, the color difference, activity, etc. were measured.

  According to the results in Table 7, ΔE increases with increasing immersion time, but the activity decreases, so that the longer the immersion time in the soaking / slow dyeing assistant, the longer the anodized aluminum by the dyeing pretreatment It shows that the slow dyeing effect of the sheet becomes stronger.

<Example 10>
In this example, the influence on the dyeing of the dyeing finishing pretreatment performed at different temperatures with the treatment solution of the anode aluminum level dyeing / loosening aid was investigated.

  The powder preparation of the anodic aluminum level dyeing / loosening aid prepared in Example 1 of the present invention was diluted to a treatment liquid having a concentration of 15 g / L (based on the concentration of the first active ingredient). After adjusting the pH of the diluted treatment liquid to 2.0, anodized aluminum sheets (model No. 5052, oxide film thickness of about 15 μm) are respectively added to the treatment liquid at temperatures of 25 ° C. and 45 ° C. for 5 minutes. It was immersed and then removed from the treatment solution and washed with deionized water. Subsequently, the aluminum sheet was immersed in a black dye (TAC Black SLH415AN) having a concentration of 10 g / L and dyed under the same conditions as described above (dye at 55 ° C. for 15 minutes). Finally, the color tone Lab value and dyeing activity of the finished product were measured. The experimental results are shown in Table 8. “Blank” in Table 8 refers to an empty sample. The empty sample was an anodic aluminum sample in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution. After dyeing, the color difference, activity, etc. were measured.

  According to the results of Table 8, when other conditions are not changed, ΔE increases with increasing temperature, but the activity decreases, so that the higher the temperature of the soaking / dyeing assistant processing solution, the higher the dyeing finish. It shows that the slow dyeing effect of the anodized aluminum sheet by pretreatment becomes stronger.

<Example 11>
During the process of anodization, a difference in anodized film thickness is often caused on the surface of an aluminum product due to non-uniform current density distribution. If the color difference caused at the time of dyeing due to the difference in the anodized film thickness is too large, surface unevenness is generated. Dyeing finishing with a leveling / slow dyeing assistant can satisfactorily solve this problem.

  The powder preparation of level dyeing / loosening aid prepared in Example 1 was diluted to a treatment liquid having a concentration of 0 g / L to 15 g / L (based on the concentration of the first active ingredient). Under the same operating conditions as above (soaked at 25 ° C. for 5 minutes), the anode aluminum test piece (aluminum material part number 5052, oxide film thickness 5 μm to 20 μm) was subjected to dyeing pretreatment and then taken out from the treatment liquid. Washed with deionized water. Subsequently, the aluminum sheet was immersed in two concentrations (0.5 g / L, 2 g / L) of black dye (TAC Black GBL 413) and dyed under the same conditions (25 ° C., pH 5.0) as described above. The length of the dyeing time depends on whether or not each sample is dyed and finished with a level dyeing / loosening aid and the concentration of the processing solution. Regardless of whether or not to carry out, as much as possible after the dyeing so that there is no great difference in color shade. For example, samples that are not pre-treated with level dyeing / loosening aids tend to be deeply dyed, so it is necessary to control the dyeing time to be short (6 minutes 30 seconds to 8 minutes), while samples that are pre-treated with level dyeing / dyeing aids are pretreated. In addition, since it takes a long time to dye the sample to the same degree of light and shade, it is necessary to dye the sample with a relatively long staining time (9 to 11 minutes) in the experiment. Finally, the color tone Lab value and the color difference ΔE of the finished product were measured. The color difference ΔE is based on the Lab value with an oxide film thickness of 10 μm. Also, the standard deviation between the anode aluminum samples treated with different levels of leveling / dyeing aid and the standard deviation σ between the anode aluminum samples not treated with leveling / slowing aid was calculated. The calculation formula of the standard deviation σ is shown below.

Formula 3

  In the formula, μ is calculated as follows.

Formula 4

  The experimental results are shown in Table 9. “0 g / L” in Table 9 refers to empty samples (total of 8 samples, each corresponding to a different oxide film thickness and staining time). The empty sample is four anodic aluminum samples with different film thicknesses, each of which had two concentrations (each 0.5 g / L), other than being immersed in the leveling / slow dyeing assistant solution and other experimental processes performed similarly. 2 g / L) was dyed with a black dye, and the color difference was measured.

  According to the results of Table 9, the samples pre-dyed with the level dyeing / loosening aid, regardless of the dye concentration (0.5 g / L or 2 g / L) at the time of dyeing, oxide film thicknesses of 5 μm, 15 μm, and 20 μm Since the color difference ΔE between this sample and the sample having a film thickness of 10 μm is relatively small and the numerical value of the standard deviation follows the same tendency, it is proved that the soaking / slow dyeing assistant has the effect of uniformly dyeing. From the overall data, the color difference when the leveling / dyeing aid concentration is 15 g / L is smaller than the color difference when the level is 6 g / L. An increase from / L to 15 g / L is shown to be advantageous for further uniform staining.

<Example 12>
In this example, the effect of the dyeing pretreatment with the level dyeing / loosening aid on uniform dyeing was investigated. The powder preparation of level dyeing / loosening aid prepared in Example 1 was diluted to a treatment liquid having a concentration of 6 g / L and 15 g / L (based on the concentration of the first active ingredient). After adjusting the pH of the diluted treatment solution to 2.0, an aluminum sheet (model number 5052, oxide film thickness 10.6 μm to 11.2 μm) is added to the above solution under different temperature (25 ° C. and 45 ° C.) conditions. It was immersed for 5 minutes, and then removed from the treatment liquid and washed with deionized water. Subsequently, the aluminum sheet was immersed in a black dye (TAC Black GBLH 413 black dye) having a concentration of 0.5 g / L, and dyed under the same conditions (25 ° C., 8 minutes dyeing, pH 5.0). Finally, the color tone Lab value and the color difference ΔE of 5 points (4 corners and midpoint of the sample) were measured for the finished product. The color difference ΔE is based on the Lab value at the midpoint. The experimental results are shown in Table 10. “Blank” in Table 10 refers to an empty sample. The empty sample was an anodic aluminum sample in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution, and after dyeing, the color difference and the like were measured.

  According to the results of Table 10, regardless of the concentration of the leveling / slow dyeing assistant (6 g / L or 15 g / L), the sample pre-stained with the leveling / slow dyeing assistant has four corners and an intermediate point. Is smaller than the blank sample, it is proved that the leveling / slow dyeing assistant has the effect of uniformly dyeing under the corresponding conditions. From the overall data, the color difference ΔE when the level of the leveling / dyeing aid is 15 g / L is slightly smaller than the color difference ΔE when the level is 6 g / L. An increase from 6 g / L to 15 g / L is shown to be advantageous for further uniform staining.

<Example 13>
The present Example investigated the effect with respect to the aluminum material of the product number from which the dyeing | staining preliminary process by a level dyeing | staining dyeing auxiliary agent differs.

  The powder preparation of leveling / loosening aid prepared in Example 1 was diluted to a treatment liquid having a concentration of 6 g / L (based on the concentration of the first active ingredient). Under the same operating conditions as above, i.e., immersed for 5 minutes at 25 [deg.] C., an anode aluminum test piece (aluminum material product number 7018, oxide film thickness of about 15 [mu] m) was subjected to dyeing pretreatment and then taken out from the processing solution. And washed with deionized water. Subsequently, the aluminum sheet was immersed in a black dye (TAC Black SLH 415AN, 10 g / L) and dyed under certain conditions (55 ° C., 15 min). Further, the color tone Lab value and the dyeing activity of the finished product were measured, and the measurement results were compared with a sample (empty sample) that was not preliminarily dyed with a level dyeing / loosening aid. The experimental results are shown in Table 11. “Blank” in Table 11 refers to an empty sample. The blank sample was an anode aluminum sample (aluminum material product number 7018) in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution, and the color difference was measured after dyeing.

  According to the results of Table 11, the sample pre-dyed with the leveling / slow dyeing assistant has a low color difference ΔE and low activity, so that it also has a slow dyeing effect on the aluminum sheet No. 7018. As shown, it proved that the anodic aluminum leveling and dyeing aid can be applied to different grades of aluminum material.

<Example 14>
In this example, when the dyeing pretreatment with the level dyeing / loosening aid was applied to anodized aluminum sheets having different film thicknesses, the color change was investigated after being irradiated with sunlight (sunshine).

  The powder preparation of the anodic aluminum leveling / loosening aid prepared in Example 1 was diluted to become treatment liquids having concentrations of 6 g / L and 15 g / L (based on the concentration of the first active ingredient). . Anodized aluminum sheet (aluminum material product number 5052, film thickness 5 μm and 10 μm, respectively) was immersed in the above treatment solution for 5 minutes at the same operating conditions as described above, that is, at 25 ° C., then taken out from the treatment solution and deionized. Washed with water. Subsequently, the aluminum sheet was immersed in a red dye (TAC Red BLH102, 10 g / L) and dyed under certain conditions (25 ° C., 5 min). Furthermore, the color tone Lab value of the finished product was measured. The dyed aluminum sheet was irradiated with a photobleaching tester (Atlas Suntest CPS +, manufactured by Atlas Co., Ltd.), taken out from the photobleaching tester at regular time intervals, and the color tone Lab value was examined. At the same time, the color difference before and after sunlight irradiation was compared. The experimental results are shown in Table 12. “Blank” in Table 12 refers to empty samples (two in total, each corresponding to a different oxide film thickness). The empty sample was an anodic aluminum sample in which other experimental processes were performed in the same manner except that it was not immersed in the soaking / slow dyeing assistant solution, and the color difference after irradiation with sunlight was measured.

  According to the results in Table 12, the aluminum sheet pretreated with the treatment solution of two levels of leveling / dyeing assistant was dyed and irradiated with sunlight for 5 months regardless of whether the anode film thickness was 5 μm or 10 μm. After that, there is no difference in the color difference ΔE compared to the sample that was not pretreated with the level dyeing / loosening aid (empty sample). It turned out that there was not much difference.

<Example 15>
In this example, the effect of dyeing pretreatment with an anodic aluminum leveling and dyeing aid on the free energy of the anodized aluminum surface was investigated.

  The powder preparation of level dyeing / loosening aid prepared in Example 1 was diluted to be treatment liquids having concentrations of 6 g / L and 15 g / L (based on the concentration of the first active ingredient). An anodized aluminum sheet (aluminum material model No. 5052, oxide film thickness of about 15 μm) is immersed in the above treatment liquid for 5 minutes at the same operating conditions as described above, that is, at 25 ° C., then taken out from the treatment liquid and deionized water. Washed with. Then, after air-drying for 30 minutes at room temperature, the contact angle of the anode aluminum surface was measured. The experimental results are shown in Table 13. “Blank” in Table 13 refers to an empty sample. An empty sample was a sample immersed in deionized water containing no soaking / slow dyeing assistant under conditions such as the same temperature and immersion time, and then the contact angle was measured.

  The larger the contact angle, the lower the free energy on the surface. According to the results in Table 13, the aluminum sheet dyed and pretreated with the level dyeing / loosening aid is in contact with the surface of the aluminum sheet regardless of whether the leveling / dyeing aid concentration is 6 g / L or 15 g / L. It has been shown that it has the effect of increasing the corners, and it is proved that the leveling / slow dyeing assistant can reduce the free energy of the aluminum sheet surface and make it difficult to adsorb other substances on the aluminum sheet surface. This is considered to be the root cause of the level dyeing / dyeing assistant that exerts the dyeing effect.

  The anodic aluminum level dyeing / dyeing assistant and the treatment solution thereof, and the anodic aluminum leveling / slow dyeing process according to the present invention have a slow dyeing effect, and the anodic aluminum oxide film thickness (the anodic aluminum film thickness is too thin). And the mechanical strength of the product tends to be insufficient), or the dyeing time (when the dyeing time is too short, the dyeing tends to be nonuniform) does not need to be reduced. The aluminum product treated with the auxiliary agent has a small color difference between products of different batches, and does not cause uneven dyeing or unevenness due to the difference in oxide film thickness due to the complicated structure of the surface of the aluminum product. The effect of can be achieved. In addition, since the auxiliary agent has a phosphorus-free composition and does not affect the sealed pores after dyeing, it can be applied to conventional anode aluminum processes and can be applied to aluminum materials of various types and product numbers. In addition, after using the auxiliary agent, the fading of the aluminum product due to sunlight irradiation was not much different from that of the untreated anodic aluminum product.

Claims (12)

Anode aluminum level dyeing / dyeing assistant,
The anode aluminum level dyeing / loosening aid includes a first active ingredient, a second active ingredient, and an auxiliary additive,
The first active ingredient includes one or more selected from carboxylic acid group-containing compounds, carboxylates, substituted carboxylates, carboxylic anhydrides, amino acid salts, and amino acid anhydrides,
The second active ingredient includes a sulfonic acid group-containing compound and / or a sulfonate.
The auxiliary additive includes one or more selected from a pH stabilizer, an antiblocking agent, and a scale inhibitor.
An anode aluminum level dyeing / dyeing assistant characterized in that. The carboxylic acid group-containing compound includes a carboxylic acid or a substituted carboxylic acid,
The substituted carboxylic acid includes an amino acid, a hydroxy acid, a halogenated acid, or a carbonyl acid.
The anode aluminum level dyeing / loosening aid according to claim 1. The amino acid is one selected from glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, aspartic acid, histidine, asparagine, glutamic acid, lysine, glutamine, methionine, arginine, serine, threonine, cysteine, and proline. Or including two or more,
The anode aluminum level dyeing / loosening aid according to claim 2. The carboxylic acid group-containing compound is acetic acid, glycolic acid, propionic acid, acrylic acid, formic acid acetic anhydride, tartaric acid, malic acid, malonic acid, lactic acid, crotonic acid, maleic acid, oxaloacetic acid, succinic acid, 1, 3-glutaric acid, α-ketoglutaric acid, 1-hexanoic acid, 1,4-adipic acid, citric acid, heptanoic acid, 1,5-pimelic acid, benzoic acid, 1,2-phthalic acid, 1,3-phthalic acid Including one or more selected from acids, 1,4-phthalic acid, salicylic acid, and monocarboxylic acid polymers or polycarboxylic acid polymers,
The anode aluminum level dyeing / loosening aid according to claim 1. The carboxylate salt includes a carboxylic acid sodium salt, a carboxylic acid potassium salt, a carboxylic acid magnesium salt, or a carboxylic acid calcium salt,
The substituted carboxylate salt includes a substituted carboxylic acid sodium salt, a substituted carboxylic acid potassium salt, a substituted carboxylic acid magnesium salt, or a substituted carboxylic acid calcium salt,
The amino acid salt includes an amino acid sodium salt, an amino acid potassium salt, an amino acid magnesium salt, or an amino acid calcium salt.
The anode aluminum level dyeing / loosening aid according to claim 1. The sulfonic acid group-containing compound includes one or more selected from methylsulfonic acid, sulfamic acid, benzenesulfonic acid, p-toluenesulfonic acid, taurine, mercaptopropanesulfonic acid, and trifluoromethanesulfonic acid,
The sulfonate salt includes a sulfonate sodium salt, potassium salt, magnesium salt, or calcium salt.
The anode aluminum level dyeing / loosening aid according to claim 1. A processing solution for anodic aluminum level dyeing / loosening aid,
The treatment liquid for the anode aluminum level dyeing / loosening aid is obtained by adding the anode aluminum level dyeing / dyeing aid according to any one of claims 1 to 6 to water and mixing uniformly.
A processing solution for an anode aluminum leveling and dyeing aid. In the treatment solution for the anodic aluminum level dyeing / loosening aid, the concentration of the first active ingredient is 0.01 g / L to 200 g / L, and the concentration of the second active ingredient is 0.5 g / L to 400 g / L, and the concentration of the auxiliary additive is 0.5 g / L to 400 g / L.
The treatment liquid for an anode aluminum level dyeing / loosening aid according to claim 7. In the treatment liquid, the concentration of the first active ingredient is 0.5 g / L to 50 g / L, the concentration of the second active ingredient is 5 g / L to 100 g / L, The concentration is 5 g / L to 100 g / L.
The treatment solution for an anode aluminum level dyeing / loosening aid according to claim 8. Anode aluminum level dyeing / dyeing process,
The anodized aluminum anodic aluminum is put into a processing solution for the anodic aluminum leveling / slow dyeing auxiliary agent according to claim 7, treated at 5 to 90 ° C. for 1 to 60 minutes, and then taken out from the processing solution. Washing step,
Performing dyeing and sealing treatment on the cleaned anode aluminum,
Anodic aluminum level dyeing / slow dyeing process. The process of treating the anode aluminum with the treatment liquid of the anode aluminum level dyeing / loosening aid is specifically to treat at 20 ° C. to 50 ° C. for 3 minutes to 8 minutes,
The anode aluminum level dyeing / slow dyeing process according to claim 10. The treatment liquid of the anode aluminum level dyeing / loosening aid is adjusted to a pH of 0.5 to 7.0,
The anode aluminum level dyeing / slow dyeing process according to claim 10.