阅读说明：本技术 一种玻璃前处理液、其配制方法及其应用 (Glass pretreatment liquid, preparation method and application thereof ) 是由 周雪松 刘嘉桥 于 2021-08-26 设计创作，主要内容包括：本发明属于玻璃处理领域,更具体地说,涉及一种玻璃前处理液、其配制方法及其应用。本发明的玻璃前处理液,以水作为溶剂,溶质包括氟盐和质量占比不低于1％的苯扎溴铵；同时,本发明的前处理液在配制过程中,配制温度需要控制在45℃以上；本发明在使用时,仅需将玻璃浸泡于前处理液中1-10min左右即可达到理想的处理效果。本发明具有强力去除玻璃表面氧化层的功效,可以去除玻璃表面发霉、暗划伤等,同时氟盐的质量占比低,具有功效强、成本低、环保等特性,功能全面,同时还可以去除锡点、脏污、暗划伤、手指印、霉点等,从而大大降低了清洗成本。(The invention belongs to the field of glass treatment, and particularly relates to a glass pretreatment liquid, a preparation method and application thereof. The glass pretreatment liquid takes water as a solvent, and a solute comprises villiaumite and benzalkonium bromide with the mass ratio of not less than 1%; meanwhile, in the preparation process of the pretreatment liquid, the preparation temperature needs to be controlled to be more than 45 ℃; when the glass pretreatment liquid is used, the ideal treatment effect can be achieved only by soaking the glass in the pretreatment liquid for about 1-10 min. The glass cleaning agent has the effect of strongly removing the oxide layer on the surface of glass, can remove mildew, dark scratches and the like on the surface of the glass, has the characteristics of strong effect, low cost, environmental protection and the like due to low mass ratio of the villiaumite, has comprehensive functions, and can remove tin spots, dirt, dark scratches, finger marks, mildew spots and the like, thereby greatly reducing the cleaning cost.)

1. A glass pretreatment liquid is characterized by at least comprising:

water;

a fluoride salt which can provide fluoride ions for the pretreatment liquid; and

benzalkonium bromide, wherein the mass ratio of the benzalkonium bromide in the pretreatment liquid is 1% -5%.

2. The glass pretreatment liquid according to claim 1, wherein: the pretreatment liquid comprises 5-35% of one or two of nitric acid and sulfuric acid.

3. The glass pretreatment liquid according to claim 1, wherein: the conductivity of the water is not higher than 2.5 mu s/cm at 25 ℃.

4. The glass pretreatment liquid according to claim 1, wherein: the mass ratio of the benzalkonium bromide in the pretreatment liquid is 1.5-2%.

5. The glass pretreatment liquid according to claim 1, wherein: the fluorine salt is one or two of ammonium bifluoride and sodium fluoride.

6. The glass pretreatment liquid according to claim 5, wherein: the pretreatment liquid comprises ammonium bifluoride and sodium fluoride;

the mass ratio of the ammonium bifluoride in the pretreatment liquid is 5-9%, and the mass ratio of the sodium fluoride in the pretreatment liquid is 3-5%.

7. The glass pretreatment liquid according to any one of claims 1 to 6, wherein: the solution temperature of the pretreatment liquid is 40-50 ℃.

8. A method for preparing a glass pretreatment liquid, characterized in that the pretreatment liquid is a glass pretreatment liquid according to any one of claims 1 to 7, and the preparation method of the pretreatment liquid comprises: adding fluoride salt and benzalkonium bromide into water in sequence, and the preparation temperature is at least 45 ℃.

9. The method for preparing a glass pretreatment liquid according to claim 8, wherein the pretreatment liquid comprises nitric acid and sulfuric acid, and the preparation method of the pretreatment liquid comprises the following steps:

s100, mixing sulfuric acid and water in equal volume or equal mass to obtain a mixed solution A; the mass concentration of the sulfuric acid is at least 98%;

s200, adding villiaumite into the mixed solution A to obtain mixed solution B;

s300, adding nitric acid into the mixed solution B to obtain a mixed solution C; the mass concentration of the nitric acid is at most 20%;

and S400, adding benzalkonium bromide into the mixed solution C to obtain the pretreatment solution.

10. Use of a glass pretreatment liquid according to any one of claims 1 to 7 for pretreating glass, wherein: the soaking time of the glass in the pretreatment liquid is 1-10 min.

Technical Field

The invention belongs to the field of glass treatment, and particularly relates to a glass pretreatment liquid, a preparation method and application thereof.

Background

On the surface of the glass, substances which are difficult to find and difficult to handle, such as mildew, mildew-proof powder adhesion, tin point adhesion, dark scratches and the like, may exist, and the substances may cause permanent bad phenomena in the etching process of the glass, thereby affecting the product yield. The glass pretreatment liquid has the capacity of treating glass surface oxides, and at present, the glass pretreatment liquid used in the market is mainly a mixed solution of hydrofluoric acid and water, has no direct removing effect on tin spots, dark scratches and mildew-proof powder, and can only remove oil stains and dirt possibly existing on the glass surface.

For example, patent document 1 discloses a method for surface treatment before etching liquid crystal display panel glass, which comprises the steps of cleaning glass with pure water, concentrated hydrofluoric acid with a concentration of 50% to 55%, fluorosilicate, fluoride salt and surfactant, and spraying the liquid crystal display glass to be etched in a mixed solution for 15 to 80 minutes, wherein the mixed solution comprises the following components in parts by weight: 5-15% of concentrated hydrofluoric acid, 55-70% of pure water, 1-15% of fluosilicate, 1-15% of fluoride salt and 0.1-1% of surfactant, so as to achieve the purpose of cleaning.

However, the pretreatment liquid in the prior art generally has the characteristics of strong solution smell and high fluorine concentration, and has high cleaning cost. Moreover, too high fluorine concentration causes the problems of difficult secondary solution treatment and insufficient safety. In addition, in the prior art, the glass usually needs to be soaked for a long time to achieve the effect of surface cleaning, which affects the production efficiency.

Patent document 1: publication No. CN105236754A, publication No. 2016-01-13, and a surface treatment method before acid etching of liquid crystal display panel glass.

Disclosure of Invention

1. Problems to be solved

Compared with the common glass pretreatment liquid, the glass pretreatment liquid has the effect of strongly removing an oxide layer on the surface of glass, can remove mildew, dark scratches and the like on the surface of the glass, has the characteristics of strong effect, low cost, environmental protection and the like, has comprehensive functions, and can remove tin spots, dirt, dark scratches, finger prints, mildew spots and the like, thereby greatly reducing the cleaning cost.

Furthermore, the invention provides a preparation method of the pretreatment liquid, wherein the preparation temperature is controlled to be more than 45 ℃, so that the effective use temperature of the pretreatment liquid can be maintained, and the dissolution speed of each component can be accelerated.

Furthermore, the invention provides the application of the pretreatment liquid, the ideal treatment effect can be achieved by soaking the glass in the pretreatment liquid for about 1-10min, the treatment time is short, and the production efficiency is improved.

2. Technical scheme

In order to solve the problems, the technical scheme adopted by the invention is as follows:

the invention provides a glass pretreatment liquid, which at least comprises:

water, commonly used common types of reagent preparation water, can be used to prepare the pretreatment liquid of the present invention, including but not limited to deionized water, high purity water, distilled water, EDI ultrapure water, and the like;

fluoride salt which can provide fluoride ions for the pretreatment liquid and accounts for not more than 15% by mass; and

benzalkonium bromide, the mass ratio of benzalkonium bromide in the pretreatment liquid is 1% -5%.

The glass pretreatment liquid takes water as a solvent, and the solute comprises villiaumite and benzalkonium bromide with the mass ratio of not less than 1%. Benzalkonium bromide is a cationic surfactant and is usually used as a bactericide and a mildew preventive, and the benzalkonium bromide with a specific content can play a corrosion inhibition role in a fluoride solution. Benzalkonium bromide ionized to DBDA in fluoride solution⁺And Br^-The large pi-bond electron cloud on the aromatic ring in the molecule can form a coordination bond with the valence layer empty orbit of a silicon atom or an ion by adsorption on the surface of glass, so that the glass pretreatment liquid phase has a good cleaning effect compared with the common glass pretreatment liquid, is low in raw material price, does not need to be cleaned for multiple times, reduces the operation time, and reduces the number of times of cleaningThe operation complexity solves the problems that the glass mildew removing agent in the market is high in price, the cleaning effect is poor, and the glass can be cleaned only by cleaning for multiple times. Moreover, the glass pretreatment liquid can remove invisible dark scratches on the surface of the glass, and brings a remarkable yield improvement effect for the back-end glass surface etching process.

Preferably, the pretreatment liquid comprises 5% -35% of one or two of nitric acid and sulfuric acid, and meanwhile, the pH of the pretreatment liquid is kept acidic, so that the treatment effect is improved. Further preferably, the pretreatment liquid comprises 5% -10% of nitric acid and 15% of sulfuric acid, a mixed solution prepared by adding the nitric acid reacts with tin spots on the surface of the glass to generate stannous nitrate, and the stannous nitrate is hydrolyzed to form tin oxide hydrate precipitate, so that the effect of removing the tin spots is achieved.

Preferably, the conductivity of the water is not higher than 2.5 μ s/cm at 25 ℃, for example, deionized water meeting the aforementioned requirements is used as a solvent, and the cost is low.

Preferably, the mass ratio of the benzalkonium bromide in the pretreatment liquid is 1.5-2%.

Preferably, the fluorine salt is one or both of ammonium bifluoride and sodium fluoride.

Preferably, when the pretreatment liquid comprises ammonium bifluoride and sodium fluoride, the mass ratio of the ammonium bifluoride in the pretreatment liquid is 5-9%, the mass ratio of the sodium fluoride in the pretreatment liquid is 3-5%, and the mass ratio of the sodium fluoride is further preferably 3.5%, which has an excellent treatment effect.

Preferably, the solution temperature of the pretreatment liquid is 40 to 50 ℃.

The invention further provides a preparation method of the glass pretreatment liquid, the pretreatment liquid is the glass pretreatment liquid, and the preparation method of the pretreatment liquid comprises the following steps: adding fluoride salt and benzalkonium bromide into water in sequence, and the preparation temperature is at least 45 ℃. The preparation temperature in the present invention is a solution temperature at the time of preparation.

Preferably, the pretreatment liquid comprises nitric acid and sulfuric acid, and the preparation steps of the pretreatment liquid are as follows:

s100, mixing sulfuric acid and water in equal volume or equal mass to obtain a mixed solution A; the mass concentration of the sulfuric acid is at least 98 percent;

s200, adding villiaumite into the mixed solution A to obtain mixed solution B;

s300, adding nitric acid into the mixed solution B to obtain a mixed solution C; the mass concentration of the nitric acid is at most 20 percent;

and S400, adding benzalkonium bromide into the mixed liquor C to obtain a pretreatment liquor.

It is worth mentioning that the dissolution can be accelerated by stirring the mixed solution during the preparation. For example, in S200

The invention further provides application of the glass pretreatment liquid to glass pretreatment, the soaking time of the glass in the pretreatment liquid is 1-10min, such as 2min, 2.3min, 5min, 5.6min, 8min and 10min, and the soaking time can be used as the soaking time of the invention, and particularly when the soaking time is 2-5min, the treatment effect is best and the treatment efficiency is highest. Further, the glass may be subjected to other conventional operations after soaking, such as drying using a dryer, etc.

3. Advantageous effects

Compared with the prior art, the glass pretreatment liquid disclosed by the invention has the advantages that water is used as a solvent, the solute comprises villiaumite and benzalkonium bromide with the mass ratio of not less than 1%, compared with the common glass pretreatment liquid, the glass pretreatment liquid has a good cleaning effect, the raw materials are cheap, multiple cleaning is not needed, the operation time is shortened, the operation complexity is reduced, and the problems that the glass mildew remover in the market is expensive, the cleaning effect is poor and the glass can be cleaned only by multiple cleaning are solved. In addition, the glass pretreatment liquid can also remove invisible dark scratches on the surface of the glass, and has an obvious effect of improving the yield of the back-end glass surface etching process. Compared with common pretreatment liquid, the cleaning agent has comprehensive functions, can remove tin spots, dirt, dark scratches, finger prints, mildew spots and the like, and greatly reduces the cleaning cost.

Furthermore, the invention provides a preparation method of the pretreatment liquid, the preparation temperature is controlled to be more than 45 ℃, the pretreatment liquid prepared by the method can effectively improve the cleaning effect of the original glass, and the cleaning is not required to be carried out for many times, so that the preparation method has wide market prospect.

Furthermore, the invention provides the application of the pretreatment liquid, the ideal treatment effect can be achieved by soaking the glass in the pretreatment liquid for about 1-10min, the treatment time is short, and the production efficiency is improved.

Drawings

FIG. 1 is a microscopic view taken by 250 times before pretreatment with the treating solution of example 1;

FIG. 2 is a microscopic view at 250 times after pretreatment with the treatment solution of example 1.

Detailed Description

The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description is to be construed as illustrative only and not restrictive, and any such modifications and variations are intended to be included within the scope of the invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Example 1

The embodiment provides a preparation method of glass pretreatment liquid, which comprises the following steps:

s100, weighing sulfuric acid according to a certain volume ratio, adding a proper amount of deionized water, and uniformly mixing to obtain a mixed solution A; wherein the mass fraction of the sulfuric acid is 98 percent;

s200, weighing ammonium bifluoride and sodium fluoride according to a certain weight ratio, adding the ammonium bifluoride and the sodium fluoride into the mixed solution A, and uniformly mixing to obtain mixed solution B;

s300, weighing nitric acid according to a certain volume ratio, adding the nitric acid into the mixed solution B, and uniformly mixing to obtain a mixed solution C;

and S400, weighing benzalkonium bromide according to a certain volume ratio, adding the benzalkonium bromide into the mixed solution C, and uniformly mixing to obtain the glass pretreatment solution.

The steps are all carried out at the temperature of more than 45 ℃, and the pretreatment liquid prepared by the steps comprises 5% of nitric acid, 15% of sulfuric acid, 5% of ammonium bifluoride, 3.5% of sodium fluoride, 2% of benzalkonium bromide and deionized water.

The pretreatment liquid prepared in the embodiment is used for pretreating glass to be etched in an etching process, the soaking time is 3min, and the treatment effect is shown in fig. 1 and 2. The glass pretreatment liquid can remove tin spots, dirt, dark scratches, finger marks, mildew spots and the like on the surface of glass, and has a remarkable effect of improving the yield of a back-stage glass surface etching process.

Example 2

The procedure of this example is essentially the same as in example 1, except that: the glass pretreatment liquid prepared in this example includes the following components: 8% of nitric acid, 15% of sulfuric acid, 9% of ammonium bifluoride, 3.5% of sodium fluoride, 2% of benzalkonium bromide and a proper amount of deionized water; wherein the temperature of the solution is controlled to be more than 45 ℃ to prepare a finished product. The glass pretreatment liquid is prepared by using nitric acid, sulfuric acid, ammonium bifluoride, sodium fluoride, benzalkonium bromide and deionized water as raw materials, so that the glass pretreatment liquid is low in price, has a good cleaning effect, does not need to be cleaned for many times, and reduces the working strength. Meanwhile, the glass to be etched is treated by the glass pretreatment liquid prepared in the embodiment, and the treatment effect is basically the same as that of embodiment 1.

Example 3

The procedure of this example is essentially the same as in example 1, except that: the glass pretreatment liquid prepared in this example includes the following components: 10% of nitric acid, 15% of sulfuric acid, 8% of ammonium bifluoride, 3.5% of sodium fluoride, 2% of benzalkonium bromide and a proper amount of deionized water; wherein the temperature of the solution is controlled to be more than 45 ℃ to prepare a finished product; the glass pretreatment liquid is prepared by using nitric acid, sulfuric acid, ammonium bifluoride, sodium fluoride, benzalkonium bromide and deionized water as raw materials, so that the glass pretreatment liquid is low in price, has a good cleaning effect, does not need to be cleaned for many times, and reduces the working strength. Meanwhile, the glass to be etched is treated by the glass pretreatment liquid prepared in the embodiment, and the treatment effect is basically the same as that of embodiment 1.

Example 4

The procedure of this example is essentially the same as in example 1, except that: the glass pretreatment liquid prepared in this example includes the following components: 15% of sulfuric acid, 7% of ammonium bifluoride, 3.5% of sodium fluoride, 2% of benzalkonium bromide and a proper amount of deionized water; wherein the temperature of the solution is controlled to be more than 45 ℃ to prepare a finished product; the glass pretreatment liquid is prepared by using nitric acid, sulfuric acid, ammonium bifluoride, sodium fluoride, benzalkonium bromide and deionized water as raw materials, so that the glass pretreatment liquid is low in price, has a good cleaning effect, does not need to be cleaned for many times, and reduces the working strength. Meanwhile, the glass to be etched is treated by the glass pretreatment liquid prepared in the embodiment, and the treatment effect is basically the same as that of embodiment 1.

Example 5

The procedure of this example is essentially the same as in example 1, except that: the glass pretreatment liquid prepared in this example includes the following components: 8% of nitric acid, 17% of sulfuric acid, 7% of ammonium bifluoride, 3.5% of sodium fluoride, 2% of benzalkonium bromide and a proper amount of deionized water; wherein the temperature of the solution is controlled to be more than 45 ℃ to prepare a finished product; the glass pretreatment liquid is prepared by using nitric acid, sulfuric acid, ammonium bifluoride, sodium fluoride, benzalkonium bromide and deionized water as raw materials, so that the glass pretreatment liquid is low in price, has a good cleaning effect, does not need to be cleaned for many times, and reduces the working strength. Meanwhile, the glass to be etched is treated by the glass pretreatment liquid prepared in the embodiment, and the treatment effect is basically the same as that of embodiment 1.

Example 6

The procedure of this example is essentially the same as in example 1, except that: the glass pretreatment liquid prepared in this example includes the following components: 20% of sulfuric acid, 9% of ammonium bifluoride, 3.5% of sodium fluoride, 2% of benzalkonium bromide and a proper amount of deionized water; wherein the temperature of the solution is controlled to be more than 45 ℃ to prepare a finished product; the glass pretreatment liquid is prepared by using nitric acid, sulfuric acid, ammonium bifluoride, sodium fluoride, benzalkonium bromide and deionized water as raw materials, so that the glass pretreatment liquid is low in price, has a good cleaning effect, does not need to be cleaned for many times, and reduces the working strength. Meanwhile, the glass to be etched is treated by the glass pretreatment liquid prepared in the embodiment, and the treatment effect is basically the same as that of embodiment 1.

Comparative example 1

The basic contents of this comparative example are the same as example 1, except that: in this comparative example, the glass pretreatment liquid included 5 wt% of benzalkonium bromide. The result of treating the glass to be etched by using the glass pretreatment liquid of the comparative example shows that the corrosion inhibition effect of the glass pretreatment liquid is reduced, and fluosilicate is attached to the surface of the glass to form a crystal point phenomenon, thereby influencing the treatment effect.

Comparative example 2

The basic contents of this comparative example are the same as example 1, except that: in this comparative example, the glass pretreatment liquid contained no benzalkonium bromide. The result of treating the glass to be etched by using the glass pretreatment liquid of the comparative example shows that the treatment effect of the glass pretreatment liquid on oil stains or other stains on the surface of the glass to be etched is obviously reduced.

More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When a quality, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.