Blackening solution, preparation method and application thereof

Abstract

The present application relates to the technical field of preparation of blackening solution, in particular to a kind of blackening solution, its preparation method and application, its preparation includes the following steps: S1.thiourea, auxiliary lye is added in deionized water, while stirring, slowly heated to 40 DEG C and keeps temperature;S2.the solution of step S1 continues to heat, keeps temperature continues to stir, to solid dissolves, again join blackening modifier and stir;S3.deionized water is added to the mixed solution obtained in step S2 and stirred, is aged in thermostat, again through microporous filter membrane pressurized filtration, obtain blackening solution.The present application corrosion inhibitor and blackening modifier synergistic effect, improve the dispersion uniformity of blackening solution, make copper surface form dense, non-light halo blackening layer and hydrophobic film, enhance blackening solution flow flatness, block the penetration of corrosive medium, avoid the blackening uneven of copper grid edge with line width 2-5 μm.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of preparation of blackening solution, in particular to a blackening solution, a preparation method and application thereof. BACKGROUND

[0002] Metal mesh conductive film (Metal-Mesh Film) as the core material of transparent conductive film realizes conductive function through extremely fine metal mesh (usually copper) and realizes transparent conduction with the extremely fine metal mesh as the conductive functional layer. The touch sensor made of the metal mesh conductive film has the characteristics of low power consumption, touch sensitivity, long service life, flexibility, waterproofness, explosion-proofness, non-pollution, etc. and is widely used in the field of touch screens. However, the copper mesh line width is only 2-5 μm, which is lower than the recognition threshold of the naked eye, but the strong light reflection characteristics of the copper mesh still form visible light halo in the light environment, which affects the display effect and user experience. Traditional blackening solution often contains phosphorus compounds (such as phosphate), and the emission thereof can cause water eutrophication (such as “red tide”). The phosphorus emission has been strictly limited in Europe, the United States and Japan (such as the requirement of Germany that the phosphorus emission is ≤1 mg / L), and phosphorus-free has become an inevitable trend in the industry. Therefore, it is urgent to develop a phosphorus-free, low-temperature, high-efficiency and copper mesh damage-free blackening solution to balance the low reflectivity (anti-halo) and conductive performance of the copper surface while meeting the environmental protection requirements. SUMMARY

[0003] In view of the deficiencies in the prior art, the present application aims to provide a blackening solution, a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0005] A preparation method of a blackening solution, comprising the following preparation steps:

[0006] S1. 2-4 parts of thiourea and 0.1-0.3 parts of auxiliary alkali solution are added into 45-50 parts of deionized water according to the mass fraction, and stirred at a speed of 200-250 r / min while slowly heating to 40℃ and keeping for 10-15 min;

[0007] S2. The solution of step S1 is continuously heated to 49-51℃, and the temperature is kept and stirred for 30-35 min until the solid is dissolved, and then 1-1.7 parts of blackening modifier is added, and stirred at a speed of 100-200 r / min for 5-10 min;

[0008] S3. 45-50 parts of deionized water is added to the mixed solution obtained in step S2, and stirred at a speed of 150-200 r / min for 20-30 min, and then aged in a thermostat for 10-12 h, and then filtered through a microporous filter under pressure to obtain a blackening solution;

[0009] The preparation of the blackening modifier comprises the following steps:

[0010] S21. In a 45℃ constant temperature water bath, 9-11 parts of fatty alcohol polyoxyethylene ether is mixed with 1.5-2.5 parts of sodium dodecyl benzene sulfonate, stirred at a speed of 150-200 r / min for 10-15 min to obtain a transparent solution;

[0011] S22. The water bath temperature is lowered to 40℃, 2-5 parts of corrosion inhibitor modifier is added, and stirred at a low speed of 100-150 r / min for 15-20 min;

[0012] S23. 0.1-0.2 parts of polydimethylsiloxane is added to the solution obtained in step S22, and after standing for 5-10 min, it is dispersed at a speed of 200-250 r / min for 2-4 min to obtain a blackening modifier.

[0013] Preferably, the preparation of the corrosion inhibitor modifier comprises the following steps:

[0014] S221. In a 40℃ water bath environment, 2-4 parts of catechol and 0.3-0.5 parts of mercaptobenzothiazole are added to 15-20 parts of ethanol solution, and stirred at a speed of 200-250 r / min for 15-20 min to obtain an organic phase solution;

[0015] S222. The water bath temperature is raised to 50℃, 0.8-1.2 parts of trisodium phosphate and 0.5-0.8 parts of sodium benzoate are added to 5-10 parts of ethanol solution, and stirred at a speed of 250-300 r / min for 10-15 min to obtain an inorganic phase solution;

[0016] S223. The organic phase solution and the inorganic phase solution are mixed and stirred at a speed of 150-200 r / min for 20-25 min, and then aged in the dark to obtain a corrosion inhibitor modifier.

[0017] Preferably, the auxiliary lye is composed of potassium carbonate, triethanolamine, and borax in a mass ratio of 1:0.5-0.8:0.3-0.5.

[0018] Preferably, the temperature rising speed in step S1 is 2℃ / min.

[0019] Preferably, the temperature in the constant temperature oven in step S3 is 24-26℃.

[0020] Preferably, the pore size of the microporous filter membrane in step S is 0.45μm.

[0021] Preferably, the pressure in step S3 is 0.2MPa.

[0022] Preferably, the time for aging in the dark is 20-24h.

[0023] A blackening solution prepared according to the preparation method.

[0024] Application of the blackening solution prepared according to the preparation method in a copper metal grid conductive film.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] 1. The corrosion inhibitor and the blackening modifier synergistically act to improve the dispersion uniformity of the blackening solution, form a dense, non-halo blackening layer and a hydrophobic film on the copper surface, enhance the flow leveling property of the blackening solution, block the penetration of corrosive media, and avoid uneven blackening of the copper grid edge with a line width of 2-5 μm.

[0027] 2. The blackening solution has the advantages of fast blackening speed, blackening temperature close to room temperature, significantly reduced reflectivity and brightness of copper, and the effects of eliminating reflection, no damage to the grid lines, and no influence on the conductive performance. BRIEF DESCRIPTION OF DRAWINGS

[0028] Fig. 1 The preparation process flow chart of the blackening solution of the present application is shown in the figure;

[0029] Fig. 2 The preparation process flow chart of the blackening modifier of the present application is shown in the figure;

[0030] Fig. 3 The preparation process flow chart of the corrosion inhibitor of the present application is shown in the figure. DETAILED DESCRIPTION

[0031] The present application will be described in detail below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.

[0032] Please refer to Figs. 1-3 The present application provides a technical solution:

[0033] Example 1

[0034] A preparation method of a blackening solution:

[0035] Before preparing the blackening solution, the corrosion inhibitor and the blackening modifier are prepared:

[0036] The preparation of the corrosion inhibitor includes the following steps:

[0037] S221. 2g of o-dihydroxybenzene and 0.3g of mercaptobenzothiazole are added to 15g of an ethanol solution under the condition of a water bath environment at 40℃, and stirred at 200r / min for 15min to obtain an organic phase solution;

[0038] S222. The water bath temperature is raised to 50°C, 0.8 g of trisodium phosphate and 0.5 g of sodium benzoate are added to 5 g of ethanol solution, and stirred at 250 r / min for 10 min to obtain an inorganic phase solution;

[0039] S223. The organic phase solution is mixed with the inorganic phase solution, stirred at 150 r / min for 20 min, and aged in the dark for 20 h to obtain the corrosion inhibitor modifier;

[0040] The preparation of the blackening modifier includes the following steps:

[0041] S21. In a 45°C constant temperature water bath, 9 g of fatty alcohol polyoxyethylene ether is mixed with 1.5 g of sodium dodecyl benzene sulfonate, stirred at 150 r / min for 10 min to obtain a transparent solution;

[0042] S22. The water bath temperature is lowered to 40°C, and 2 g of the corrosion inhibitor modifier is added, and stirred at 100 r / min for 15 min;

[0043] S23. 0.1 g of polydimethylsiloxane is added to the solution obtained in step S22, and after standing for 5 min, it is dispersed at 200 r / min for 2 min to obtain the blackening modifier;

[0044] S1. 2 g of thiourea and 0.1 g of auxiliary lye (potassium carbonate: triethanolamine: borax = 1:0.5:0.3) are added to 45 ml of deionized water, stirred at 200 r / min, and heated to 40°C at a rate of 2°C / min and kept for 10 min;

[0045] S2. The solution of step S1 is continuously heated to 49°C, and stirred for 30 min to dissolve the solid, and then 1 g of the blackening modifier is added, and stirred at 100 r / min for 5 min;

[0046] S3. 45 ml of deionized water is added to the mixture obtained in step S2, and stirred at 150 r / min for 20 min, aged in a 24°C constant temperature box for 10 h, then filtered by 0.45 μm microporous filter under pressure, pressure 0.2 MPa, to obtain the blackening liquid.

[0047] Example 2

[0048] A method for preparing a blackening liquid:

[0049] Before preparing the blackening liquid, the corrosion inhibitor modifier and the blackening modifier are prepared:

[0050] The preparation of the corrosion inhibitor modifier includes the following steps:

[0051] S221.4g catechol and 0.5g mercaptobenzothiazole were added into 20g ethanol solution under 40℃ water bath environment, stirred at 250r / min for 20min to obtain an organic phase solution;

[0052] S222. The water bath temperature was increased to 50℃, 1.2g trisodium phosphate and 0.8g sodium benzoate were added into 10g ethanol solution, stirred at 300r / min for 15min to obtain an inorganic phase solution;

[0053] S223. The organic phase solution and the inorganic phase solution were mixed, stirred at 200r / min for 25min, and then aged in dark for 24h to obtain the corrosion inhibitor modifier;

[0054] The preparation of the blackening modifier comprises the following steps:

[0055] S21. In a 45℃ constant temperature water bath, 11g fatty alcohol polyoxyethylene ether and 2.5g sodium dodecyl benzene sulfonate were mixed, stirred at 200r / min for 15min to obtain a transparent solution;

[0056] S22. The water bath temperature was decreased to 40℃, 5g corrosion inhibitor modifier was added, and stirred at 150r / min for 20min;

[0057] S23. 0.2g polydimethylsiloxane was added to the solution obtained in step S22, and after standing for 10min, it was dispersed at 250r / min for 4min to obtain the blackening modifier;

[0058] S1. 4g thiourea and 0.3g auxiliary alkali solution (potassium carbonate: triethanolamine: borax = 1:0.8:0.5) were added into 50ml deionized water, stirred at 250r / min while increasing the temperature to 40℃ at a rate of 2℃ / min and keeping the temperature for 15min;

[0059] S2. The solution of step S1 was continuously heated to 51℃, and stirred for 35min to dissolve the solid, then 1.7g blackening modifier was added, and stirred at 200r / min for 10min;

[0060] S3. 50ml deionized water was added to the mixture obtained in step S2, stirred at 200r / min for 30min, aged in a 26℃ constant temperature box for 12h, then filtered by 0.45μm microporous filter membrane under pressure, the pressure was 0.2MPa, to obtain the blackening liquid.

[0061] Example 3

[0062] A method for preparing a blackening liquid:

[0063] Before preparing the blackening liquid, the corrosion inhibitor modifier and the blackening modifier were prepared:

[0064] The preparation of the corrosion inhibitor modifier comprises the following steps:

[0065] S221. 3g of o-benzene-diol and 0.4g of mercaptobenzothiazole are added to a 16g ethanol solution under a water bath environment at 40℃, and stirred at 220r / min for 16min to obtain an organic phase solution;

[0066] S222. The water bath temperature is increased to 50℃, 0.9g of trisodium phosphate and 0.6g of sodium benzoate are added to a 6g ethanol solution, and stirred at 270r / min for 11min to obtain an inorganic phase solution;

[0067] S223. The organic phase solution and the inorganic phase solution are mixed, and stirred at a speed of 170r / min for 22min, and then aged in the dark for 21h to obtain the corrosion inhibitor modifier;

[0068] The preparation of the blackening modifier comprises the following steps:

[0069] S21. 10g of fatty alcohol polyoxyethylene ether and 1.7g of sodium dodecyl benzene sulfonate are mixed in a constant temperature water bath at 45℃, and stirred at a speed of 170r / min for 11min to obtain a transparent solution;

[0070] S22. The water bath temperature is decreased to 40℃, and 3g of the corrosion inhibitor modifier is added, and stirred at a low speed of 120r / min for 17min;

[0071] S23. 0.12g of polydimethylsiloxane is added to the solution obtained in step S22, and after standing for 6min, dispersed at 220r / min for 3min to obtain the blackening modifier;

[0072] S1. 3g of thiourea and 0.2g of auxiliary alkali solution (potassium carbonate: triethanolamine: borax = 1:0.6:0.4) are added to 46ml of deionized water, and stirred at a speed of 220r / min while increasing the temperature to 40℃ at a rate of 2℃ / min and maintaining the temperature for 12min;

[0073] S2. The solution of step S1 is continuously heated to 50℃, and stirred for 32min to dissolve the solid, and then 1.1g of the blackening modifier is added, and stirred at a speed of 150r / min for 6min;

[0074] S3. 47ml of deionized water is added to the mixed solution obtained in step S2, and stirred at a speed of 170r / min for 22min, and then aged in a constant temperature box at 25℃ for 11h, and then filtered by pressurized filtration through a 0.45μm microporous filter membrane at a pressure of 0.2MPa to obtain the blackening solution.

[0075] Example 4

[0076] A preparation method of a blackening solution

[0077] Before preparing the blackening solution, first prepare the corrosion inhibitor modifier and the blackening modifier:

[0078] The preparation of the corrosion inhibitor modifier comprises the following steps:

[0079] S221. 3.5g of o-benzene-diol and 0.45g of mercaptobenzothiazole are added to 18g of an ethanol solution under a water bath environment of 40℃, and stirred at 240r / min for 18min to obtain an organic phase solution;

[0080] S222. The water bath temperature is increased to 50℃, 1.1g of trisodium phosphate and 0.7g of sodium benzoate are added to 9g of an ethanol solution, and stirred at 280r / min for 14min to obtain an inorganic phase solution;

[0081] S223. The organic phase solution and the inorganic phase solution are mixed, and stirred at a speed of 180r / min for 24min, and then aged in the dark for 23h to obtain the corrosion inhibitor modifier;

[0082] The preparation of the blackening modifier comprises the following steps:

[0083] S21. In a constant temperature water bath of 45℃, 10.5g of fatty alcohol polyoxyethylene ether and 2.2g of sodium dodecyl benzene sulfonate are mixed, and stirred at a speed of 180r / min for 14min to obtain a transparent solution;

[0084] S22. The water bath temperature is decreased to 40℃, and 4g of the corrosion inhibitor modifier is added, and stirred at a low speed of 140r / min for 18min;

[0085] S23. 0.18g of polydimethylsiloxane is added to the solution obtained in step S22, and after standing for 8min, dispersed at 240r / min for 3.5min to obtain the blackening modifier;

[0086] S1. 3.5g of thiourea and 0.25g of auxiliary alkali solution (potassium carbonate: triethanolamine: borax = 1:0.7:0.45) are added to 48ml of deionized water, and stirred at a speed of 220r / min while increasing the temperature to 40℃ at a rate of 2℃ / min and maintaining the temperature for 14min;

[0087] S2. The solution of step S1 is continuously heated to 50℃, and stirred for 34min to dissolve the solid, and then 1.6g of the blackening modifier is added, and stirred at a speed of 180r / min for 8min;

[0088] S3. To the mixed solution obtained in step S2, 48 ml of deionized water was added, stirred at a speed of 180 r / min for 26 min, aged in a 25°C constant temperature box for 11.5 h, and then filtered under pressure through a 0.45 μm microporous filter membrane at a pressure of 0.2 MPa to obtain a blackening solution.

[0089] Comparative Example 1

[0090] Comparative Example 1 and Example 1 only have the following differences, and the only difference is that no corrosion inhibitor modifier is added in Comparative Example 1, and the remaining steps are completely the same in Comparative Example 1 and Example 1.

[0091] Comparative Example 2

[0092] Comparative Example 2 and Example 1 only have the following differences, and the only difference is that no corrosion inhibitor modifier and blackening modifier are added in Comparative Example 2, and the remaining steps are completely the same in Comparative Example 2 and Example 1.

[0093] Performance test:

[0094] The blackening solutions obtained in Examples 1-4 and Comparative Examples 1-2 were applied to metal mesh conductive films, and reflectivity, corrosion resistance, hydrophobicity, and conductivity were tested respectively. According to GB / T 9754-2007 “Color Paint and Varnish Determination of Mirror Gloss”, a BYK-micro-TRI-gloss multi-angle gloss meter was used to measure the reflectivity of 550 nm visible light at an incident angle of 60°, and 9 points were measured for each group to take the average value. According to GB / T 10125-2021 “Artificial Atmosphere Corrosion Test Salt Spray Test”, 5% NaCl solution was used to continuously spray at 35°C for 24 h, and the number of corrosion points at the edge of the mesh was observed using a microscope, and the corrosion area ratio was calculated. The contact angle of deionized water was measured by the sessile drop method, and 5 points were measured for each sample to take the average value. The sheet resistance was measured according to the four-point probe method, and the sheet resistance change rate before and after blackening was calculated, and the calculation formula was: (R 后 -R 前 ) / R 前 ×100%. The final data is shown in Table 1:

[0095] Table 1

[0096]

[0097] From the data in the table, the reflectivity, corrosion resistance, hydrophobicity, and conductivity of the examples are significantly better than those of the comparative examples, proving that the synergistic effect of the corrosion inhibitor modifier and the blackening modifier can effectively fill the copper grain boundary defects, the blackening agent optimizes the leveling property, and together solves the blackening problem at the edge of the micron-level mesh, reduces the reflectivity and brightness of copper, and achieves the effect of shadow elimination. At the same time, the phosphorus-free formula in the present application meets the emission standards of Europe and the United States.

[0098] While embodiments of the application have been shown and described, it is to be understood that the embodiments described are merely exemplary of the principles and application of the present application. Numerous modifications and adaptions can be effected without departing from the spirit and scope of the present application, which is not limited to the exact construction and arrangement described. It is intended, therefore, to cover all modifications and adaptions that fall within the scope of the claims and their equivalents.

Claims

1. A method for preparing a blackening solution, characterized by, The preparation method comprises the following steps: S1. 2-4 parts of thiourea and 0.1-0.3 parts of auxiliary alkali liquor are added into 45-50 parts of deionized water, and stirring is carried out at a rotating speed of 200-250 r / min, then the temperature is slowly increased to 40℃ and kept for 10-15 min; S2. The solution of step S1 is continuously heated to 49-51℃, and stirring is continuously carried out at the temperature for 30-35 min until the solid is dissolved, then 1-1.7 parts of blackening modifier is added, and stirring is carried out at a rotating speed of 100-200 r / min for 5-10 min; S3. 45-50 parts of deionized water is added into the mixed solution obtained in step S2, and stirring is carried out at a rotating speed of 150-200 r / min for 20-30 min, then 10-12 h of aging is carried out in a thermostat, then pressure filtration is carried out through a microporous filter membrane to obtain a blackening solution; The preparation of the blackening modifier comprises the following steps: S21. 9-11 parts of fatty alcohol polyoxyethylene ether and 1.5-2.5 parts of sodium dodecyl benzene sulfonate are mixed in a 45℃ constant temperature water bath, and stirring is carried out at a rotating speed of 150-200 r / min for 10-15 min to obtain a transparent solution; S22. The water bath temperature is reduced to 40℃, 2-5 parts of corrosion modification agent is added, and stirring is carried out at a low speed of 100-150 r / min for 15-20 min; S23. 0.1-0.2 parts of polydimethylsiloxane is added into the solution obtained in step S22, and after standing for 5-10 min, dispersion is carried out at a rotating speed of 200-250 r / min for 2-4 min to obtain the blackening modifier.

2. The method of claim 1, wherein the blackening solution is prepared by adding the reducing agent to the acidic solution. The preparation of the corrosion modification agent comprises the following steps: S221. 2-4 parts of catechol and 0.3-0.5 parts of mercaptobenzothiazole are added into 15-20 parts of ethanol solution in a water bath environment at 40℃, and stirring is carried out at a rotating speed of 200-250 r / min for 15-20 min to obtain an organic phase solution; S222. The water bath temperature is increased to 50℃, 0.8-1.2 parts of trisodium phosphate and 0.5-0.8 parts of sodium benzoate are added into 5-10 parts of ethanol solution, and stirring is carried out at a rotating speed of 250-300 r / min for 10-15 min to obtain an inorganic phase solution; S223. The organic phase solution and the inorganic phase solution are mixed, and stirring is carried out at a rotating speed of 150-200 r / min for 20-25 min, and the corrosion modification agent is obtained after light aging.

3. The method of claim 1, wherein the blackening solution is prepared by adding 0.5 to 2.5 g of the blackening agent to 100 ml of the acidic solution. The auxiliary alkali liquor is composed of potassium carbonate, triethanolamine and borax with a mass ratio of 1:0.5-0.8:0.3-0.

5.

4. The method of claim 1, wherein the blackening solution is prepared by adding 0.5 to 1.5 g of the blackening agent to 100 ml of the acidic solution. The temperature increasing speed of the slow temperature increasing in step S1 is 2℃ / min.

5. The method of claim 1, wherein the blackening solution is prepared by adding 0.5 to 2.5 g of the blackening agent to 100 ml of the acidic solution. The temperature in the thermostat in step S3 is 24-26℃.

6. The method of claim 1, wherein the blackening solution is prepared by adding 0.5 to 2.5 g of the blackening agent to 100 ml of the acidic solution. The pore size of the microporous filter membrane in step S is 0.45μm.

7. The method of claim 1, wherein the blackening solution is prepared by adding 0.5 to 2.5 g of the blackening agent to 100 ml of the acidic solution. The pressure in step S3 is 0.2MPa.

8. The method of claim 2, wherein the blackening solution is prepared by adding 0.5 to 1.5 g of the blackening agent to 100 ml of the acidic solution. The light aging time is 20-24h.

9. A blackening solution prepared by the preparation method in any one of claims 1-8.

10. Application of the blackening solution in claim 9 in a copper metal mesh conductive film.

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