WO2016011708A1 - Sapphire glass etching solution and method for etching sapphire glass - Google Patents

Sapphire glass etching solution and method for etching sapphire glass Download PDF

Info

Publication number
WO2016011708A1
WO2016011708A1 PCT/CN2014/088466 CN2014088466W WO2016011708A1 WO 2016011708 A1 WO2016011708 A1 WO 2016011708A1 CN 2014088466 W CN2014088466 W CN 2014088466W WO 2016011708 A1 WO2016011708 A1 WO 2016011708A1
Authority
WO
WIPO (PCT)
Prior art keywords
sapphire glass
etching
acid
sapphire
etching solution
Prior art date
Application number
PCT/CN2014/088466
Other languages
French (fr)
Chinese (zh)
Inventor
陈志雄
杨顺林
廖昌
刘昆
Original Assignee
深圳市宇顺电子股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳市宇顺电子股份有限公司 filed Critical 深圳市宇顺电子股份有限公司
Publication of WO2016011708A1 publication Critical patent/WO2016011708A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/20—Aluminium oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08—Etching
    • C30B33/10—Etching in solutions or melts

Definitions

  • the invention belongs to the field of sapphire glass etching, and in particular relates to a sapphire glass etching solution and a sapphire glass etching method.
  • Sapphire is a generic name for corundum gemstones in addition to red rubies in corundum gemstones.
  • the main component is alumina (Al 2 O 3 ).
  • SAPPHIRE CRYSTAL generally refers to synthetic sapphire, which is very different from the natural sapphire that people usually understand.
  • Sapphire glass has the following characteristics: hardness is 9, which is higher than ordinary glass; it can be produced by adding various chemical elements; sapphire glass has good thermal properties, excellent electrical properties and dielectric properties, and Anti-chemical corrosion, high temperature resistance, good heat conduction, transparent infrared, good chemical stability.
  • sapphire glass makes it ideal for high-end products, such as the mirror used to make high-end watches, for the cover glass and back cover of high-end smartphones.
  • the traditional sapphire processing process is polished by physical grinding, but because sapphire is high in hardness and brittle, it is very difficult to machine it, and it is more difficult to process sapphire glass into mirror processing that meets the requirements of high-end watches and high-end smartphones.
  • the main problems faced by the sapphire glass processing industry are as follows: the collapse and collapse angle in the processing process, the defect rate is 5 ⁇ 8%; the surface scratches after sapphire grinding and polishing; the low yield and difficult to rework, resulting in the price of finished sapphire glass No high.
  • the purpose of the embodiments of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a sapphire glass etching solution for chemical etching of sapphire glass, which avoids the disadvantages of etching the sapphire glass by physical processing.
  • Another object of the embodiments of the present invention is to provide a method for etching sapphire glass by using the above sapphire glass etching solution, thereby avoiding the disadvantages of etching the sapphire glass by physical processing.
  • a sapphire glass etchant consisting of the following components by weight: 20-30% hydrochloric acid, 10-15% phosphoric acid, 5-10% acetic acid, 2 ⁇ 5% sodium chloride And pure water 40 ⁇ 63%.
  • a sapphire glass etching method comprising: components in the following percentage by weight: hydrochloric acid 20-30%, phosphoric acid 10-15%, acetic acid 5-10%, sodium chloride 2 ⁇ 5%, and pure water 40 ⁇ 63% preparation of sapphire glass etching solution; sapphire glass is etched using the sapphire glass etching solution.
  • the sapphire glass etching solution of the above embodiment has a reasonable ratio, and the sapphire glass etched by the sapphire glass etching solution is excellent in quality, uniform in uniformity, and high in yield.
  • the sapphire glass etching method used in the sapphire glass etching method of the above embodiment has a reasonable ratio of sapphire glass etching liquid, and the etching method has high safety, high controllability, high quality, uniformity and high yield of the prepared product.
  • FIG. 1 is a flow chart of a sapphire glass etching method according to an embodiment of the present invention.
  • Embodiments of the present invention provide a sapphire glass etching solution.
  • the sapphire glass etching solution is composed of the following components by weight: 20-30% hydrochloric acid, 10-15% phosphoric acid, 5-10% acetic acid, sodium chloride 2 ⁇ 5% and pure water 40 ⁇ 63%.
  • the weight percentage of hydrochloric acid if the weight percentage of hydrochloric acid is less than 20%, the production efficiency is low; if the weight percentage of hydrochloric acid is more than 30%, the production control difficulty is increased, and the defective product is easily produced. Therefore, the above comparison is reasonable, which can ensure a certain production efficiency, and can accurately control the reaction rate, and the quality of the product produced by the sapphire glass etching solution is high.
  • the hydrochloric acid in the formulation of the sapphire glass etching solution of the embodiment of the present invention is used for reacting with alumina, iron oxide, and titanium oxide which are main components of sapphire glass. If hydrochloric acid is replaced by sulfuric acid or nitric acid, there is a hazard: sulfuric acid has strong water absorption, which leads to an uncontrollable increase in reaction rate; higher concentration of nitric acid and faster reaction rate increase the difficulty of production control. Therefore, the use of sulfuric acid and nitric acid and the sapphire cover plate has a poor controllability and affects product quality, so hydrochloric acid is preferred as the formulation of the sapphire glass etchant.
  • Sodium chloride ensures the concentration of chloride ions
  • phosphoric acid ensures hydrogen ion concentration, and ensures reaction rate.
  • the sapphire glass etching solution is preferably sodium chloride.
  • Acetic acid ensures ionization equilibrium of the etchant while providing hydrogen ions.
  • NaCl ⁇ Na + +Cl - sodium chloride ionization ensures chloride ion concentration.
  • CH 3 COOH ⁇ CH 3 COO - + H + , acetic acid also provides hydrogen ions by ionization.
  • the AlO 2 - , Fe(OH) 3 and TiO 2 ⁇ xH 2 O produced by the hydrolysis are liable to adhere to the surface of the sapphire glass to prevent further reaction of the hydrochloric acid and the sapphire glass. Therefore, by adding sodium chloride, phosphoric acid and acetic acid to ensure the chloride ion concentration and the hydrogen ion concentration, respectively, the hydrolysis reaction of AlCl 3 , FeCl 3 and TiCl 4 tends to be reversed, thereby avoiding AlO 2 - and Fe produced by hydrolysis ( OH) 3 and TiO 2 ⁇ xH 2 O are attached to the surface of the sapphire glass, affecting the rate of the reaction.
  • the mass percentage of HCl in hydrochloric acid is 15 to 50%
  • the mass percentage of H 3 PO 4 in phosphoric acid is 15 to 50%
  • the mass percentage of CH 3 COOH in acetic acid is 30 to 98%.
  • the sapphire glass etching solution is arranged as follows: firstly, pure water is added to the liquid mixing tank, then sodium chloride, hydrochloric acid and phosphoric acid are added, and finally acetic acid is added, mixed and stirred uniformly to prepare a sapphire glass etching solution.
  • the liquid mixing environment requires constant temperature, the temperature is 22 ⁇ 28 °C, and the humidity is 50%.
  • the final addition of acetic acid is required to prevent excessive hydrolysis of acetic acid and affect the concentration of H+.
  • FIG. 1 is a flow chart of a sapphire glass etching method according to an embodiment of the present invention.
  • the sapphire glass etching method of the embodiment of the invention includes:
  • Step S01 preparing a sapphire glass etching solution.
  • hydrochloric acid 20 ⁇ 30%, phosphoric acid 10 ⁇ 15%, acetic acid 5 ⁇ 10%, sodium chloride 2 ⁇ 5% and pure water 40 ⁇ 63% weigh the raw materials, mix and stir evenly Prepare a sapphire glass etchant.
  • the mass percentage of HCl in hydrochloric acid is 15 to 50%
  • the mass percentage of H 3 PO 4 in phosphoric acid is 15 to 50%
  • the mass percentage of CH 3 COOH in acetic acid is 30 to 98%.
  • Step S02 etching the sapphire glass with a sapphire glass etching solution.
  • the etching time can be selected according to the concentration of the sapphire glass etching solution, the etching temperature, and the etching amount.
  • the sapphire glass etching method used in the sapphire glass etching method of the embodiment of the invention has reasonable ratio, high safety, high controllability, high quality, uniformity and high yield of the prepared product.
  • the acid-resistant film or the acid-resistant peelable adhesive may be used to protect the glass from the portion to be etched prior to etching the sapphire glass.
  • This application is not limited thereto, and other reagents may be used to protect the sapphire glass from etching. This step is not necessary if all parts of the sapphire glass require etching.
  • the sapphire glass etching device is an etching groove, and the sapphire glass etching solution is injected into the etching groove to etch the sapphire glass.
  • the etching bath has the following characteristics: the etching bath is immersed in the etched tank under the condition of full sealing, and the pressure in the tank is negative pressure, so that the production installation is more secure, and the gas overflow of the liquid in the etching tank is avoided; the important parts of the tank body For example, the inner tank is made of iron hibiscus, and other minor parts are made of acid-resistant organic plastic; the etching tank is provided with a circulating liquid supply device, and a new sapphire glass etching solution is regularly injected to ensure the concentration of the sapphire glass etching solution, so that the groove The concentration and height of the internal drug solution can be controlled and the production stability is higher.
  • a filter is arranged in the circulation device to filter the crystals of aluminum chloride, ferric chloride and titanium chloride generated during the etching process, thereby avoiding the adhesion of the crystal body.
  • the surface of the sapphire glass product affects the production; a constant temperature control device is provided in the etching bath to control the temperature difference in the etching bath and the temperature of the etching solution.
  • the application is not limited thereto, and other suitable etching equipment may be used for sapphire glass etching.
  • the temperature of the sapphire glass etching solution is 20 ° C to 60 ° C, and the temperature difference in the etching bath (that is, the temperature difference of the etching liquid in the etching tank) is controlled within 5%. If the temperature is lower than 20 ° C, the production efficiency of the sapphire glass etching process is low; if the temperature is higher than 60 ° C, the etching rate of the sapphire glass etching process is accelerated, which increases the difficulty of production control and is easy to produce defective products.
  • the temperature difference in the etching bath is controlled within 5% to ensure a more uniform etching, and the quality of the etched sapphire glass is better. If the temperature difference in the etching bath is too large, uneven etching may occur, resulting in defective products.
  • the etching rate of the etched sapphire glass is 0.01 to 0.015 mm/min. If the etch rate is less than 0.01 Mm/min will reduce the production efficiency; if the etching rate is higher than 0.015 mm/min, it will increase the difficulty of production control and easily produce defective products. Therefore, the etching rate not only achieves production efficiency, but also ensures production controllability and product quality.
  • the sapphire glass etching solution and the sapphire glass etching method described above are exemplified by a plurality of embodiments.
  • composition by weight percent: 20% hydrochloric acid with 15% HCl, 10% phosphoric acid with 15% H 3 PO 4 , 5% acetic acid with 30% CH 3 COOH, chlorination Sodium 2% and pure water 63% were weighed, mixed and stirred uniformly to prepare a sapphire glass etching solution.
  • the sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath.
  • the temperature of the sapphire glass etchant was kept at 45 ⁇ 3° C., and the temperature difference in the etching bath was controlled within 5%.
  • the sapphire glass was etched using an etch rate of 0.01 mm/min.
  • the etching solution of Example 1 etched sapphire glass at an etching rate of 0.01 mm/min, which not only ensured production efficiency but also ensured etching precision and production controllability.
  • the etching time of Example 1 was 3 to 7 min, and the etching amount was 0.03 to 0.07 mm.
  • the etching time is set to 5 min and the etching amount is 0.05 mm.
  • the conventional sapphire cover is etched, the original piece to be etched is placed in the basket, and the basket is placed in the etching bath.
  • the size of the basket and the etching groove can be designed according to the actual production capacity while ensuring the uniformity of the concentration of the chemical solution in the etching tank.
  • the smallest baskets commonly used can hold 60 sapphire glass, and the baskets designed for mass production can hold up to 1400-1600 sapphire glass.
  • the dimensional tolerance is generally 0.005 mm.
  • the sapphire glass after the etching in Example 1 had no chipping angle, and the dimensional tolerance of each of the length and width directions was ⁇ 0.0001 mm, and the etching yield was >98%.
  • the prior art uses a polishing and flat grinding process to process sapphire glass, and the yield is generally ⁇ 70%. Therefore, the formulation ratio of the first embodiment is reasonable, the preparation method has high safety, high controllability in production, excellent quality of the prepared product, good uniformity, and high yield.
  • the etch rate of the sapphire glass etchant of this formulation is suitable for edge treatment and micro-processing of sapphire glass.
  • HCl mass fraction of 50% hydrochloric acid 30%, H 3 PO 4 15% mass fraction of 50% phosphoric acid, CH 3 COOH 98% mass fraction of 10% acetic acid chloride Sodium 2% and pure water 43% were weighed, mixed and stirred to prepare a sapphire glass etching solution.
  • Protect the sapphire glass from etched areas with an anti-strong acid film or an anti-strong acid peelable adhesive The sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath.
  • the temperature of the sapphire glass etchant was kept at 45 ⁇ 3° C., and the temperature difference in the etching bath was controlled within 5%.
  • the sapphire glass was etched using an etch rate of 0.015 mm/min.
  • the etching time of Example 2 was 3 to 7 minutes, and the etching amount was 0.03 to 0.07 mm.
  • the etching time is set to 5 min and the etching amount is 0.05 mm.
  • the sapphire glass after the etching in Example 2 had no chipping angle, and the dimensional tolerance of each of the length and width directions was ⁇ 0.0001 mm, and the etching yield was >98%.
  • the sapphire glass is processed by polishing and flat grinding, and the yield is generally ⁇ 70%. Therefore, the formulation ratio of the embodiment 2 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has excellent quality, good uniformity and high yield.
  • the etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
  • HCl mass fraction of 37% hydrochloric acid 25%, H 3 PO 4 12% mass fraction of 35% phosphoric acid, CH 3 COOH 50% mass fraction of 8% acetic acid chloride Sodium 3% and pure water 52% were weighed, mixed and stirred uniformly to prepare a sapphire glass etching solution.
  • HCl mass fraction of 37% hydrochloric acid 25%, H 3 PO 4 12% mass fraction of 35% phosphoric acid, CH 3 COOH 50% mass fraction of 8% acetic acid chloride Sodium 3% and pure water 52% were weighed, mixed and stirred uniformly to prepare a sapphire glass etching solution.
  • the sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath.
  • the temperature of the sapphire glass etchant was kept at 45 ⁇ 3° C., and the temperature difference in the etching bath was controlled within 5%.
  • the sapphire glass was etched using an etch rate of 0.012 mm/min.
  • the etching time is 3 to 7 minutes, and the etching amount is 0.03 to 0.07 mm.
  • the etching time is set to 4 min and the etching amount is 0.05 mm.
  • the sapphire glass after the etching in Example 3 had no chipping angle, and the dimensional tolerance of each of the length and width directions was ⁇ 0.0001 mm, and the etching yield was >98%.
  • the sapphire glass is processed by polishing and flat grinding, and the yield is generally ⁇ 70%.
  • the formulation ratio of the embodiment 3 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has good quality, good uniformity and high yield.
  • the etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
  • the raw material was weighed by 5% sodium and 40% pure water, mixed and stirred uniformly to prepare a sapphire glass etching solution.
  • the sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath.
  • the temperature of the sapphire glass etching solution was kept at 20 ° C, and the temperature difference in the etching bath was controlled within 5%.
  • the sapphire glass was etched using an etch rate of 0.012 mm/min.
  • the etching time is 3 to 7 minutes, and the etching amount is 0.03 to 0.07 mm.
  • the etching time is set to 4 min and the etching amount is 0.05 mm.
  • the sapphire glass after the etching in Example 4 had no chipping angle, and the dimensional tolerance of each of the length and width directions was ⁇ 0.0001 mm, and the etching yield was >98%.
  • the sapphire glass is processed by polishing and flat grinding, and the yield is generally ⁇ 70%.
  • the formulation ratio of the embodiment 4 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has good quality, good uniformity and high yield.
  • the etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
  • the temperature of the sapphire glass etching solution was kept at 60 ° C, and the temperature difference in the etching bath was controlled within 5%.
  • the sapphire glass was etched using an etch rate of 0.012 mm/min.
  • the etching time is 3 to 7 minutes, and the etching amount is 0.03 to 0.07 mm.
  • the etching time is set to 4 min and the etching amount is 0.05 mm.
  • the sapphire glass after the etching in Example 5 had no chipping angle, and the dimensional tolerance of each of the length and width directions was ⁇ 0.0001 mm, and the etching yield was >98%.
  • the sapphire glass is processed by polishing and flat grinding, and the yield is generally ⁇ 70%.
  • the formulation ratio of the embodiment 5 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has good quality, good uniformity and high yield.
  • the etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
  • the sapphire glass etching solution and the sapphire glass etching method of the embodiment of the invention are suitable for thinning processing of sapphire glass, edge treatment of sapphire glass, punching and grooving of sapphire glass, and solving the collapse of physical processing of sapphire glass. Key issues such as flaking angles and scratches.
  • the formulation of the sapphire glass etchant is reasonable.
  • the sapphire glass etching method has high safety, high controllability in production, excellent quality, uniformity and high yield of the prepared product.

Abstract

Provided is a sapphire glass etching solution. The sapphire glass etching solution is composed of the following components by weight content in percentage: 20-30% of hydrochloric acid, 10-15% of phosphoric acid, 5-10% of acetic acid, 2-5% of sodium chloride and 40-63% of pure water. A method for etching a sapphire glass, comprising: preparing a sapphire glass etching solution with the following components by weight content in percentage: 20-30% of hydrochloric acid, 10-15% of phosphoric acid, 5-10% of acetic acid, 2-5% of sodium chloride and 40-63% of pure water; and etching the sapphire glass using the sapphire glass etching liquid. The sapphire glass etching solution in embodiments of the present invention has a rational ratio. The method for etching a sapphire glass in embodiments of the present invention has high safety and high controllability of production. The sapphire glass etched by the sapphire glass etching solution has an excellent quality, good homogeneity and a high yield, avoiding drawbacks resulting from etching the sapphire glass by a physical processing method.

Description

蓝宝石玻璃蚀刻液及蓝宝石玻璃蚀刻方法  Sapphire glass etching solution and sapphire glass etching method 技术领域Technical field
本发明属于蓝宝石玻璃蚀刻领域，具体涉及一种蓝宝石玻璃蚀刻液及蓝宝石玻璃蚀刻方法。The invention belongs to the field of sapphire glass etching, and in particular relates to a sapphire glass etching solution and a sapphire glass etching method.
背景技术Background technique
蓝宝石是刚玉宝石中除红色的红宝石之外，其它颜色刚玉宝石的通称，主要成分是氧化铝（Al2O3）。蓝宝石玻璃（SAPPHIRE CRYSTAL）一般是指人工合成的蓝宝石，与人们平常理解的珠宝——天然蓝宝石有着很大的区别。Sapphire is a generic name for corundum gemstones in addition to red rubies in corundum gemstones. The main component is alumina (Al 2 O 3 ). SAPPHIRE CRYSTAL generally refers to synthetic sapphire, which is very different from the natural sapphire that people usually understand.
蓝宝石玻璃有以下特点：硬度为9，较普通玻璃硬度更高；可以通过添加各种化学元素，生成各种颜色；蓝宝石玻璃有很好的热特性，极好的电气特性和介电特性，并且防化学腐蚀，耐高温，导热好，透红外，化学稳定性好。Sapphire glass has the following characteristics: hardness is 9, which is higher than ordinary glass; it can be produced by adding various chemical elements; sapphire glass has good thermal properties, excellent electrical properties and dielectric properties, and Anti-chemical corrosion, high temperature resistance, good heat conduction, transparent infrared, good chemical stability.
蓝宝石玻璃以上特点决定了其非常适合用于高端产品，比如用于制作高档手表的表镜，用于高档智能手机的盖板玻璃及后盖。传统的蓝宝石加工工艺是通过物理研磨抛光，但由于蓝宝石硬度高且脆性大，对其进行机械加工非常困难，而将蓝宝石玻璃加工成符合高档手表及高档智能手机要求的镜面加工工艺则更加困难。目前，蓝宝石玻璃加工行业面临主要问题如下：加工过程中出现崩边崩角，不良率5~8%；蓝宝石研磨抛光后出现表面刮伤；因良率低且难以返工，导致蓝宝石玻璃成品价格居高不下。The above characteristics of sapphire glass make it ideal for high-end products, such as the mirror used to make high-end watches, for the cover glass and back cover of high-end smartphones. The traditional sapphire processing process is polished by physical grinding, but because sapphire is high in hardness and brittle, it is very difficult to machine it, and it is more difficult to process sapphire glass into mirror processing that meets the requirements of high-end watches and high-end smartphones. At present, the main problems faced by the sapphire glass processing industry are as follows: the collapse and collapse angle in the processing process, the defect rate is 5~8%; the surface scratches after sapphire grinding and polishing; the low yield and difficult to rework, resulting in the price of finished sapphire glass No high.
技术问题technical problem
本发明实施例的目的在于克服现有技术的上述不足，提供一种用于蓝宝石玻璃化学蚀刻的蓝宝石玻璃蚀刻液，避免采用物理加工方法蚀刻蓝宝石玻璃所带来的弊端。The purpose of the embodiments of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a sapphire glass etching solution for chemical etching of sapphire glass, which avoids the disadvantages of etching the sapphire glass by physical processing.
本发明实施例的另一目的在于提供一种采用上述蓝宝石玻璃蚀刻液蚀刻蓝宝石玻璃的方法，避免采用物理加工方法蚀刻蓝宝石玻璃所带来的弊端。Another object of the embodiments of the present invention is to provide a method for etching sapphire glass by using the above sapphire glass etching solution, thereby avoiding the disadvantages of etching the sapphire glass by physical processing.
技术解决方案Technical solution
为了实现上述发明目的，本发明实施例的技术方案如下：In order to achieve the above object, the technical solution of the embodiment of the present invention is as follows:
一种蓝宝石玻璃蚀刻液，所述蓝宝石玻璃蚀刻液由按以下重量百分含量计的成分组成：盐酸20~30%、磷酸10~15%、醋酸5~10%、氯化钠2~5%和纯水40~63%。A sapphire glass etchant consisting of the following components by weight: 20-30% hydrochloric acid, 10-15% phosphoric acid, 5-10% acetic acid, 2~5% sodium chloride And pure water 40~63%.
以及，一种蓝宝石玻璃蚀刻方法，包括：按以下重量百分含量计的成分：盐酸20~30%、磷酸10~15%、醋酸5~10%、氯化钠2~5%和纯水40~63%制备蓝宝石玻璃蚀刻液；采用所述蓝宝石玻璃蚀刻液蚀刻蓝宝石玻璃。And a sapphire glass etching method comprising: components in the following percentage by weight: hydrochloric acid 20-30%, phosphoric acid 10-15%, acetic acid 5-10%, sodium chloride 2~5%, and pure water 40 ~63% preparation of sapphire glass etching solution; sapphire glass is etched using the sapphire glass etching solution.
有益效果Beneficial effect
上述实施例的蓝宝石玻璃蚀刻液的配比合理，采用该蓝宝石玻璃蚀刻液蚀刻的蓝宝石玻璃的品质优良，均匀性好，良率高。 The sapphire glass etching solution of the above embodiment has a reasonable ratio, and the sapphire glass etched by the sapphire glass etching solution is excellent in quality, uniform in uniformity, and high in yield.
上述实施例的蓝宝石玻璃蚀刻方法采用的蓝宝石玻璃蚀刻液配比合理，该蚀刻方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。The sapphire glass etching method used in the sapphire glass etching method of the above embodiment has a reasonable ratio of sapphire glass etching liquid, and the etching method has high safety, high controllability, high quality, uniformity and high yield of the prepared product.
附图说明DRAWINGS
下面将结合附图及实施例对本发明作进一步说明，附图中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, in which:
图1为本发明实施例的蓝宝石玻璃蚀刻方法的流程图。1 is a flow chart of a sapphire glass etching method according to an embodiment of the present invention.
本发明的实施方式Embodiments of the invention
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明实施例提供一种蓝宝石玻璃蚀刻液。该蓝宝石玻璃蚀刻液由按以下重量百分含量计的成分组成：盐酸20~30%、磷酸10~15%、醋酸5~10%、氯化钠2~ 5%和纯水40~63%。Embodiments of the present invention provide a sapphire glass etching solution. The sapphire glass etching solution is composed of the following components by weight: 20-30% hydrochloric acid, 10-15% phosphoric acid, 5-10% acetic acid, sodium chloride 2~ 5% and pure water 40~63%.
在该配方组成下，如盐酸的重量百分含量小于20%，则生产效率较低；如盐酸的重量百分含量大于30%，则会增加生产控制难度，容易产出不良品。因此，上述配比较为合理，既能保证一定的生产效率，又可做到精确控制反应速率，用该蓝宝石玻璃蚀刻液生产的产品品质较高。Under the composition of the formula, if the weight percentage of hydrochloric acid is less than 20%, the production efficiency is low; if the weight percentage of hydrochloric acid is more than 30%, the production control difficulty is increased, and the defective product is easily produced. Therefore, the above comparison is reasonable, which can ensure a certain production efficiency, and can accurately control the reaction rate, and the quality of the product produced by the sapphire glass etching solution is high.
本发明实施例的蓝宝石玻璃蚀刻液的配方中的盐酸用于与蓝宝石玻璃的主要成分氧化铝、氧化铁、氧化钛反应。如果将盐酸替换为硫酸或者硝酸，则会有如下的危害：硫酸有较强的吸水性，会导致反应速率不可控性增加；硝酸浓度较高，反应速度较快，会增加生产控制难度。因此，采用硫酸和硝酸与蓝宝石盖板的反应速率可控性差，会影响产品品质，所以优选盐酸作为该蓝宝石玻璃蚀刻液的配方。氯化钠保证氯离子的浓度，磷酸保证氢离子浓度，并保证反应速度。氯化钠虽然也可用其他金属氯化物代替，但相应会带来成本的增加，因此该蓝宝石玻璃蚀刻液优选为氯化钠。醋酸保证蚀刻液的电离平衡，同时提供氢离子。The hydrochloric acid in the formulation of the sapphire glass etching solution of the embodiment of the present invention is used for reacting with alumina, iron oxide, and titanium oxide which are main components of sapphire glass. If hydrochloric acid is replaced by sulfuric acid or nitric acid, there is a hazard: sulfuric acid has strong water absorption, which leads to an uncontrollable increase in reaction rate; higher concentration of nitric acid and faster reaction rate increase the difficulty of production control. Therefore, the use of sulfuric acid and nitric acid and the sapphire cover plate has a poor controllability and affects product quality, so hydrochloric acid is preferred as the formulation of the sapphire glass etchant. Sodium chloride ensures the concentration of chloride ions, phosphoric acid ensures hydrogen ion concentration, and ensures reaction rate. Although sodium chloride can be replaced by other metal chlorides, there is a corresponding increase in cost, and therefore the sapphire glass etching solution is preferably sodium chloride. Acetic acid ensures ionization equilibrium of the etchant while providing hydrogen ions.
本发明所涉及到的化学反应方程式如下：The chemical reaction equations referred to in the present invention are as follows:
NaCl→Na++Cl-，氯化钠电离保证氯离子浓度。H3PO4→3H++PO4 3-，磷酸电离保证氢离子浓度。CH3COOH→CH3COO-+H+，醋酸也通过电离提供氢离子。NaCl→Na + +Cl - , sodium chloride ionization ensures chloride ion concentration. H 3 PO 4 →3H + +PO 4 3- , phosphoric acid ionization ensures hydrogen ion concentration. CH 3 COOH → CH 3 COO - + H + , acetic acid also provides hydrogen ions by ionization.
蓝宝石玻璃中的氧化铝、氧化铁、氧化钛分别与盐酸反应：Al2O3 + 6HCl = 2AlCl3 + 3H2O、Fe2O3 + 6HCl = 2FeCl3 + 3H2O和TiO2 + 4HCl = TiCl4 + 2H2O。Alumina, iron oxide and titanium oxide in sapphire glass are respectively reacted with hydrochloric acid: Al 2 O 3 + 6HCl = 2AlCl 3 + 3H 2 O, Fe 2 O 3 + 6HCl = 2FeCl 3 + 3H 2 O and TiO 2 + 4HCl = TiCl 4 + 2H 2 O.
由于在水溶液中，AlCl3、FeCl3和TiCl4均易发生如下的水解反应：Since AlCl 3 , FeCl 3 and TiCl 4 are all susceptible to the following hydrolysis reactions in aqueous solution:
AlCl3+ 3 H2O<——> AlO2 -+ 3HCl + H3O+ AlCl 3 + 3 H 2 O<——> AlO 2 - + 3HCl + H 3 O +
FeCl3+3H2O <——> Fe(OH)3+3HClFeCl 3 +3H 2 O <——> Fe(OH) 3 +3HCl
TiCl4 + (x+2)H2O<——> TiO2·xH2O + 4HClTiCl 4 + (x+2)H 2 O<——> TiO 2 ·xH 2 O + 4HCl
水解产生的AlO2 -、Fe(OH)3和TiO2·xH2O等易附着在蓝宝石玻璃表面，阻止盐酸和蓝宝石玻璃的进一步反应。因此，通过加入氯化钠、磷酸和醋酸分别保证氯离子浓度和氢离子浓度，使AlCl3 、FeCl3和TiCl4的水解反应更倾向于逆向进行，从而避免水解产生的 AlO2 - 、Fe(OH)3 和TiO2·xH2O 等附着在蓝宝石玻璃表面，影响反应的速率。The AlO 2 - , Fe(OH) 3 and TiO 2 ·xH 2 O produced by the hydrolysis are liable to adhere to the surface of the sapphire glass to prevent further reaction of the hydrochloric acid and the sapphire glass. Therefore, by adding sodium chloride, phosphoric acid and acetic acid to ensure the chloride ion concentration and the hydrogen ion concentration, respectively, the hydrolysis reaction of AlCl 3 , FeCl 3 and TiCl 4 tends to be reversed, thereby avoiding AlO 2 - and Fe produced by hydrolysis ( OH) 3 and TiO 2 ·xH 2 O are attached to the surface of the sapphire glass, affecting the rate of the reaction.
优选的，盐酸中HCl的质量百分含量为15~50%，磷酸中H3PO4的质量百分含量为15~50%，醋酸中CH3COOH的质量百分含量为30~98%。Preferably, the mass percentage of HCl in hydrochloric acid is 15 to 50%, the mass percentage of H 3 PO 4 in phosphoric acid is 15 to 50%, and the mass percentage of CH 3 COOH in acetic acid is 30 to 98%.
该蓝宝石玻璃蚀刻液的配置方法如下：先在配液槽中加入纯水，然后加入氯化钠、盐酸和磷酸，最后加入醋酸，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。配液环境要求恒温，温度为22~28℃，湿度为50%。醋酸需要最后加入，可以防止醋酸过度水解，影响H+的浓度。The sapphire glass etching solution is arranged as follows: firstly, pure water is added to the liquid mixing tank, then sodium chloride, hydrochloric acid and phosphoric acid are added, and finally acetic acid is added, mixed and stirred uniformly to prepare a sapphire glass etching solution. The liquid mixing environment requires constant temperature, the temperature is 22~28 °C, and the humidity is 50%. The final addition of acetic acid is required to prevent excessive hydrolysis of acetic acid and affect the concentration of H+.
如图1所示，为本发明实施例的蓝宝石玻璃蚀刻方法的流程图。本发明实施例的蓝宝石玻璃蚀刻方法包括： FIG. 1 is a flow chart of a sapphire glass etching method according to an embodiment of the present invention. The sapphire glass etching method of the embodiment of the invention includes:
步骤S01：制备蓝宝石玻璃蚀刻液。Step S01: preparing a sapphire glass etching solution.
按以下重量百分含量计的成分：盐酸20~30%、磷酸10~15%、醋酸5~10%、氯化钠2~5%和纯水40~63%称取原料，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。优选的，盐酸中HCl的质量百分含量为15~50%，磷酸中H3PO4的质量百分含量为15~50%，醋酸中CH3COOH的质量百分含量为30~98%。According to the following weight percentage components: hydrochloric acid 20~30%, phosphoric acid 10~15%, acetic acid 5~10%, sodium chloride 2~5% and pure water 40~63%, weigh the raw materials, mix and stir evenly Prepare a sapphire glass etchant. Preferably, the mass percentage of HCl in hydrochloric acid is 15 to 50%, the mass percentage of H 3 PO 4 in phosphoric acid is 15 to 50%, and the mass percentage of CH 3 COOH in acetic acid is 30 to 98%.
步骤S02：采用蓝宝石玻璃蚀刻液蚀刻蓝宝石玻璃。蚀刻时间可根据蓝宝石玻璃蚀刻液的浓度、蚀刻的温度以及蚀刻量选择。Step S02: etching the sapphire glass with a sapphire glass etching solution. The etching time can be selected according to the concentration of the sapphire glass etching solution, the etching temperature, and the etching amount.
本发明实施例的蓝宝石玻璃蚀刻方法采用的蓝宝石玻璃蚀刻液配比合理，安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。The sapphire glass etching method used in the sapphire glass etching method of the embodiment of the invention has reasonable ratio, high safety, high controllability, high quality, uniformity and high yield of the prepared product.
优选的，在蚀刻蓝宝石玻璃之前，可以使用抗酸膜或抗酸可剥胶保护玻璃无需蚀刻的部位。本申请并不以此为限，也可以采用其他试剂保护蓝宝石玻璃无需蚀刻的部位。如果蓝宝石玻璃的全部部位都需要蚀刻，则无需采用这一步骤。Preferably, the acid-resistant film or the acid-resistant peelable adhesive may be used to protect the glass from the portion to be etched prior to etching the sapphire glass. This application is not limited thereto, and other reagents may be used to protect the sapphire glass from etching. This step is not necessary if all parts of the sapphire glass require etching.
优选的，蓝宝石玻璃蚀刻的设备为蚀刻槽，将蓝宝石玻璃蚀刻液注入蚀刻槽内蚀刻蓝宝石玻璃。该蚀刻槽具有如下特点：采用蚀刻液在全封闭的条件下浸泡蚀刻槽，槽内压力为负压，使得生产安装更有保障，也避免蚀刻槽内药液挥发的气体外溢；槽体重要部件，如内槽均使用铁芙蓉制作，其他次要部件，采用耐酸碱有机塑料制作；蚀刻槽设置有循环供液装置，定时注入新蓝宝石玻璃蚀刻液，保证蓝宝石玻璃蚀刻液的浓度，使得槽内药液的浓度和高度均可控，生产稳定性更高；同时，在循环装置中设置过滤器，过滤蚀刻过程中产生的氯化铝、氯化铁、氯化钛结晶体，避免结晶体附着在蓝宝石玻璃产品表面，影响生产；蚀刻槽内设置有恒温控制装置，用以控制蚀刻槽内的温差及蚀刻液的温度。本申请并不以此为限，也可以采用其他适合的蚀刻设备进行蓝宝石玻璃蚀刻。Preferably, the sapphire glass etching device is an etching groove, and the sapphire glass etching solution is injected into the etching groove to etch the sapphire glass. The etching bath has the following characteristics: the etching bath is immersed in the etched tank under the condition of full sealing, and the pressure in the tank is negative pressure, so that the production installation is more secure, and the gas overflow of the liquid in the etching tank is avoided; the important parts of the tank body For example, the inner tank is made of iron hibiscus, and other minor parts are made of acid-resistant organic plastic; the etching tank is provided with a circulating liquid supply device, and a new sapphire glass etching solution is regularly injected to ensure the concentration of the sapphire glass etching solution, so that the groove The concentration and height of the internal drug solution can be controlled and the production stability is higher. At the same time, a filter is arranged in the circulation device to filter the crystals of aluminum chloride, ferric chloride and titanium chloride generated during the etching process, thereby avoiding the adhesion of the crystal body. The surface of the sapphire glass product affects the production; a constant temperature control device is provided in the etching bath to control the temperature difference in the etching bath and the temperature of the etching solution. The application is not limited thereto, and other suitable etching equipment may be used for sapphire glass etching.
优选的，蓝宝石玻璃蚀刻的过程中，蓝宝石玻璃蚀刻液的温度为20℃~60℃，蚀刻槽内的温差（即蚀刻槽内各处的蚀刻液的温差）控制在5%以内。如果温度低于20℃，则该蓝宝石玻璃蚀刻过程的生产效率较低；如温度高于60℃，则该蓝宝石玻璃蚀刻过程的蚀刻速率加快，增加了生产控制难度，容易产出不良品。蚀刻槽内的温差控制在5%以内，可以保证蚀刻更为均匀，蚀刻的蓝宝石玻璃的品质较好。如果该蚀刻槽内的温差过大，则会造成蚀刻不均，产生不良品。Preferably, during the etching of the sapphire glass, the temperature of the sapphire glass etching solution is 20 ° C to 60 ° C, and the temperature difference in the etching bath (that is, the temperature difference of the etching liquid in the etching tank) is controlled within 5%. If the temperature is lower than 20 ° C, the production efficiency of the sapphire glass etching process is low; if the temperature is higher than 60 ° C, the etching rate of the sapphire glass etching process is accelerated, which increases the difficulty of production control and is easy to produce defective products. The temperature difference in the etching bath is controlled within 5% to ensure a more uniform etching, and the quality of the etched sapphire glass is better. If the temperature difference in the etching bath is too large, uneven etching may occur, resulting in defective products.
优选的，蚀刻蓝宝石玻璃的蚀刻速率为0.01~0.015mm/min。如果蚀刻速率小于0.01 mm/min，则会降低生产效率；如果蚀刻速率高于0.015mm/min，则会增加生产可控性难度，容易生产出不良品。因此，该蚀刻速率既兼顾了生产效率，又能保证生产可控性和产品品质。Preferably, the etching rate of the etched sapphire glass is 0.01 to 0.015 mm/min. If the etch rate is less than 0.01 Mm/min will reduce the production efficiency; if the etching rate is higher than 0.015 mm/min, it will increase the difficulty of production control and easily produce defective products. Therefore, the etching rate not only achieves production efficiency, but also ensures production controllability and product quality.
以下通过多个实施例来举例说明上述蓝宝石玻璃蚀刻液及蓝宝石玻璃蚀刻方法。The sapphire glass etching solution and the sapphire glass etching method described above are exemplified by a plurality of embodiments.
实施例1 Example 1
按以下重量百分含量计的成分：HCl质量分数为15%的盐酸20%、H3PO4质量分数为15%的磷酸10%、CH3COOH质量分数为30%的醋酸5%、氯化钠2%、纯水63%称取原料，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。使用抗强酸膜或抗强酸可剥胶保护蓝宝石玻璃无需蚀刻的部位。将蓝宝石玻璃蚀刻液注入蚀刻槽中，然后将待蚀刻的蓝宝石玻璃投入蚀刻槽中蚀刻。蚀刻过程中，保持蓝宝石玻璃蚀刻液的温度为45±3℃，蚀刻槽内温差控制在5%以内。采用0.01mm/min的蚀刻速率蚀刻蓝宝石玻璃。实施例1的蚀刻液以0.01mm/min的蚀刻速率蚀刻蓝宝石玻璃，既能保证生产效率，又能保证蚀刻精度和生产可控性。实施例1的蚀刻时间为3~7min，蚀刻量为0.03~0.07mm。优选的，蚀刻时间设置为5min，蚀刻量为0.05mm。Composition by weight percent: 20% hydrochloric acid with 15% HCl, 10% phosphoric acid with 15% H 3 PO 4 , 5% acetic acid with 30% CH 3 COOH, chlorination Sodium 2% and pure water 63% were weighed, mixed and stirred uniformly to prepare a sapphire glass etching solution. Protect the sapphire glass from etched areas with an anti-strong acid film or an anti-strong acid peelable adhesive. The sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath. During the etching process, the temperature of the sapphire glass etchant was kept at 45±3° C., and the temperature difference in the etching bath was controlled within 5%. The sapphire glass was etched using an etch rate of 0.01 mm/min. The etching solution of Example 1 etched sapphire glass at an etching rate of 0.01 mm/min, which not only ensured production efficiency but also ensured etching precision and production controllability. The etching time of Example 1 was 3 to 7 min, and the etching amount was 0.03 to 0.07 mm. Preferably, the etching time is set to 5 min and the etching amount is 0.05 mm.
常规的蓝宝石盖板蚀刻，将待蚀刻的原片放入篮具中，再将篮具放入蚀刻槽中。篮具大小和蚀刻槽可以在保证蚀刻槽内药液浓度均匀性的情况下，根据实际产能进行设计。常用的最小篮具可以放置60片蓝宝石玻璃，大批量生产所设计的篮具最多可以放置1400~1600片蓝宝石玻璃。现有技术中，蓝宝石玻璃切割后，尺寸公差一般为0.005mm。The conventional sapphire cover is etched, the original piece to be etched is placed in the basket, and the basket is placed in the etching bath. The size of the basket and the etching groove can be designed according to the actual production capacity while ensuring the uniformity of the concentration of the chemical solution in the etching tank. The smallest baskets commonly used can hold 60 sapphire glass, and the baskets designed for mass production can hold up to 1400-1600 sapphire glass. In the prior art, after sapphire glass is cut, the dimensional tolerance is generally 0.005 mm.
实施例1蚀刻后的蓝宝石玻璃无崩边崩角,长宽方向各自的尺寸公差＜0.0001mm，蚀刻良率＞98%。现有技术采用抛光、平磨工艺加工蓝宝石玻璃，良率一般＜70%。因此，实施例1的配方配比合理，制备方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。该配方的蓝宝石玻璃蚀刻液的蚀刻速率适合蓝宝石玻璃的边缘处理及微处理。The sapphire glass after the etching in Example 1 had no chipping angle, and the dimensional tolerance of each of the length and width directions was <0.0001 mm, and the etching yield was >98%. The prior art uses a polishing and flat grinding process to process sapphire glass, and the yield is generally <70%. Therefore, the formulation ratio of the first embodiment is reasonable, the preparation method has high safety, high controllability in production, excellent quality of the prepared product, good uniformity, and high yield. The etch rate of the sapphire glass etchant of this formulation is suitable for edge treatment and micro-processing of sapphire glass.
实施例2 Example 2
按以下重量百分含量计的成分：HCl质量分数为50%的盐酸30%、H3PO4 质量分数为50%的磷酸15%、CH3COOH 质量分数为98%的醋酸10%、氯化钠2%、纯水43%称取原料，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。使用抗强酸膜或抗强酸可剥胶保护蓝宝石玻璃无需蚀刻的部位。将蓝宝石玻璃蚀刻液注入蚀刻槽中，然后将待蚀刻的蓝宝石玻璃投入蚀刻槽中蚀刻。蚀刻过程中，保持蓝宝石玻璃蚀刻液的温度为45±3℃，蚀刻槽内温差控制在5%以内。采用0.015mm/min的蚀刻速率蚀刻蓝宝石玻璃。实施例2的蚀刻时间为3~7min，蚀刻量为0.03~0.07mm。优选的，蚀刻时间设置为5min，蚀刻量为0.05mm。Meter in the following weight percent composition: HCl mass fraction of 50% hydrochloric acid 30%, H 3 PO 4 15% mass fraction of 50% phosphoric acid, CH 3 COOH 98% mass fraction of 10% acetic acid chloride Sodium 2% and pure water 43% were weighed, mixed and stirred to prepare a sapphire glass etching solution. Protect the sapphire glass from etched areas with an anti-strong acid film or an anti-strong acid peelable adhesive. The sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath. During the etching process, the temperature of the sapphire glass etchant was kept at 45±3° C., and the temperature difference in the etching bath was controlled within 5%. The sapphire glass was etched using an etch rate of 0.015 mm/min. The etching time of Example 2 was 3 to 7 minutes, and the etching amount was 0.03 to 0.07 mm. Preferably, the etching time is set to 5 min and the etching amount is 0.05 mm.
实施例2蚀刻后的蓝宝石玻璃无崩边崩角,长宽方向各自的尺寸公差＜0.0001mm，蚀刻良率＞98%。采用抛光、平磨工艺加工蓝宝石玻璃，良率一般＜70%。因此，实施例2的配方配比合理，制备方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。该配方的蓝宝石蚀刻液的蚀刻速率适合蓝宝石玻璃的边缘处理及减薄加工。The sapphire glass after the etching in Example 2 had no chipping angle, and the dimensional tolerance of each of the length and width directions was <0.0001 mm, and the etching yield was >98%. The sapphire glass is processed by polishing and flat grinding, and the yield is generally <70%. Therefore, the formulation ratio of the embodiment 2 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has excellent quality, good uniformity and high yield. The etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
实施例3 Example 3
按以下重量百分含量计的成分：HCl质量分数为37%的盐酸25%、H3PO4 质量分数为35%的磷酸12%、CH3COOH 质量分数为50%的醋酸8%、氯化钠3%、纯水52%称取原料，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。使用抗强酸膜或抗强酸可剥胶保护蓝宝石玻璃无需蚀刻的部位。将蓝宝石玻璃蚀刻液注入蚀刻槽中，然后将待蚀刻的蓝宝石玻璃投入蚀刻槽中蚀刻。蚀刻过程中，保持蓝宝石玻璃蚀刻液的温度为45±3℃，蚀刻槽内温差控制在5%以内。采用0.012mm/min的蚀刻速率蚀刻蓝宝石玻璃。蚀刻时间为3~7min，蚀刻量为0.03~0.07mm。优选的，蚀刻时间设置为4min，蚀刻量为0.05mm。Meter in the following weight percent composition: HCl mass fraction of 37% hydrochloric acid 25%, H 3 PO 4 12% mass fraction of 35% phosphoric acid, CH 3 COOH 50% mass fraction of 8% acetic acid chloride Sodium 3% and pure water 52% were weighed, mixed and stirred uniformly to prepare a sapphire glass etching solution. Protect the sapphire glass from etched areas with an anti-strong acid film or an anti-strong acid peelable adhesive. The sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath. During the etching process, the temperature of the sapphire glass etchant was kept at 45±3° C., and the temperature difference in the etching bath was controlled within 5%. The sapphire glass was etched using an etch rate of 0.012 mm/min. The etching time is 3 to 7 minutes, and the etching amount is 0.03 to 0.07 mm. Preferably, the etching time is set to 4 min and the etching amount is 0.05 mm.
实施例3蚀刻后的蓝宝石玻璃无崩边崩角,长宽方向各自的尺寸公差＜0.0001mm，蚀刻良率＞98%。而采用抛光、平磨工艺加工蓝宝石玻璃，良率一般＜70%。实施例3的配方配比合理，制备方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。该配方的蓝宝石蚀刻液的蚀刻速率适合蓝宝石玻璃的边缘处理及减薄加工。The sapphire glass after the etching in Example 3 had no chipping angle, and the dimensional tolerance of each of the length and width directions was <0.0001 mm, and the etching yield was >98%. The sapphire glass is processed by polishing and flat grinding, and the yield is generally <70%. The formulation ratio of the embodiment 3 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has good quality, good uniformity and high yield. The etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
实施例4 Example 4
按以下重量百分含量计的成分：HCl质量分数为20%的盐酸30%、H3PO4 质量分数为18%的磷酸15%、CH3COOH 质量分数为40%的醋酸10%、氯化钠5%、纯水40%称取原料，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。使用抗强酸膜或抗强酸可剥胶保护蓝宝石玻璃无需蚀刻的部位。将蓝宝石玻璃蚀刻液注入蚀刻槽中，然后将待蚀刻的蓝宝石玻璃投入蚀刻槽中蚀刻。蚀刻过程中，保持蓝宝石玻璃蚀刻液的温度为20℃，蚀刻槽内温差控制在5%以内。采用0.012mm/min的蚀刻速率蚀刻蓝宝石玻璃。蚀刻时间为3~7min，蚀刻量为0.03~0.07mm。优选的，蚀刻时间设置为4min，蚀刻量为0.05mm。Meter in the following weight percent composition: HCl mass fraction of 30% 20% hydrochloric acid, H 3 PO 4 15% mass fraction of 18% phosphoric acid, CH 3 COOH 40% mass fraction of 10% acetic acid chloride The raw material was weighed by 5% sodium and 40% pure water, mixed and stirred uniformly to prepare a sapphire glass etching solution. Protect the sapphire glass from etched areas with an anti-strong acid film or an anti-strong acid peelable adhesive. The sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath. During the etching process, the temperature of the sapphire glass etching solution was kept at 20 ° C, and the temperature difference in the etching bath was controlled within 5%. The sapphire glass was etched using an etch rate of 0.012 mm/min. The etching time is 3 to 7 minutes, and the etching amount is 0.03 to 0.07 mm. Preferably, the etching time is set to 4 min and the etching amount is 0.05 mm.
实施例4蚀刻后的蓝宝石玻璃无崩边崩角,长宽方向各自的尺寸公差＜0.0001mm，蚀刻良率＞98%。而采用抛光、平磨工艺加工蓝宝石玻璃，良率一般＜70%。实施例4的配方配比合理，制备方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。该配方的蓝宝石蚀刻液的蚀刻速率适合蓝宝石玻璃的边缘处理及减薄加工。The sapphire glass after the etching in Example 4 had no chipping angle, and the dimensional tolerance of each of the length and width directions was <0.0001 mm, and the etching yield was >98%. The sapphire glass is processed by polishing and flat grinding, and the yield is generally <70%. The formulation ratio of the embodiment 4 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has good quality, good uniformity and high yield. The etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
实施例5Example 5
按以下重量百分含量计的成分：HCl质量分数为40%的盐酸28%、H3PO4 质量分数为30%的磷酸12%、CH3COOH 质量分数为80%的醋酸6%、氯化钠4%、纯水50%称取原料，混合并搅拌均匀，制备得到蓝宝石玻璃蚀刻液。使用抗强酸膜或抗强酸可剥胶保护蓝宝石玻璃无需蚀刻的部位。将蓝宝石玻璃蚀刻液注入蚀刻槽中，然后将待蚀刻的蓝宝石玻璃投入蚀刻槽中蚀刻。蚀刻过程中，保持蓝宝石玻璃蚀刻液的温度为60℃，蚀刻槽内温差控制在5%以内。采用0.012mm/min的蚀刻速率蚀刻蓝宝石玻璃。蚀刻时间为3~7min，蚀刻量为0.03~0.07mm。优选的，蚀刻时间设置为4min，蚀刻量为0.05mm。Ingredients in terms of weight percent: 28% hydrochloric acid with a HCl mass fraction of 28%, 12% phosphoric acid with a 30% mass fraction of H 3 PO 4 , 6% acetic acid with a mass fraction of 80% CH 3 COOH, chlorination Sodium 4% and pure water 50% were weighed, mixed and stirred uniformly to prepare a sapphire glass etching solution. Protect the sapphire glass from etched areas with an anti-strong acid film or an anti-strong acid peelable adhesive. The sapphire glass etching solution is injected into the etching bath, and then the sapphire glass to be etched is etched into the etching bath. During the etching process, the temperature of the sapphire glass etching solution was kept at 60 ° C, and the temperature difference in the etching bath was controlled within 5%. The sapphire glass was etched using an etch rate of 0.012 mm/min. The etching time is 3 to 7 minutes, and the etching amount is 0.03 to 0.07 mm. Preferably, the etching time is set to 4 min and the etching amount is 0.05 mm.
实施例5蚀刻后的蓝宝石玻璃无崩边崩角,长宽方向各自的尺寸公差＜0.0001mm，蚀刻良率＞98%。而采用抛光、平磨工艺加工蓝宝石玻璃，良率一般＜70%。实施例5的配方配比合理，制备方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。该配方的蓝宝石蚀刻液的蚀刻速率适合蓝宝石玻璃的边缘处理及减薄加工。The sapphire glass after the etching in Example 5 had no chipping angle, and the dimensional tolerance of each of the length and width directions was <0.0001 mm, and the etching yield was >98%. The sapphire glass is processed by polishing and flat grinding, and the yield is generally <70%. The formulation ratio of the embodiment 5 is reasonable, the preparation method has high safety, the production controllability is high, the prepared product has good quality, good uniformity and high yield. The etch rate of the sapphire etchant of this formulation is suitable for edge treatment and thinning of sapphire glass.
综上所述，本发明实施例的蓝宝石玻璃蚀刻液和蓝宝石玻璃蚀刻方法适合蓝宝石玻璃的减薄加工、蓝宝石玻璃边缘处理、蓝宝石玻璃的打孔、挖槽加工，解决了蓝宝石玻璃物理加工的崩边崩角、刮伤等关键问题。该蓝宝石玻璃蚀刻液的配方的配比合理。该蓝宝石玻璃蚀刻方法的安全性高，生产可控性高，制备的产品的品质优良，均匀性好，良率高。In summary, the sapphire glass etching solution and the sapphire glass etching method of the embodiment of the invention are suitable for thinning processing of sapphire glass, edge treatment of sapphire glass, punching and grooving of sapphire glass, and solving the collapse of physical processing of sapphire glass. Key issues such as flaking angles and scratches. The formulation of the sapphire glass etchant is reasonable. The sapphire glass etching method has high safety, high controllability in production, excellent quality, uniformity and high yield of the prepared product.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包括在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (10)

  1. 一种蓝宝石玻璃蚀刻液，其特征在于，所述蓝宝石玻璃蚀刻液由按以下重量百分含量计的成分组成：盐酸20~30%、磷酸10~15%、醋酸5~10%、氯化钠2~5%和纯水40~63%。 A sapphire glass etching solution, characterized in that the sapphire glass etching solution is composed of the following components by weight: 20-30% hydrochloric acid, 10-15% phosphoric acid, 5-10% acetic acid, sodium chloride 2~5% and pure water 40~63%.
  2. 如权利要求1所述的蓝宝石玻璃蚀刻液，其特征在于：所述盐酸中HCl的质量百分含量为15~50%，所述磷酸中H3PO4 的质量百分含量为15~50%，所述醋酸中CH3COOH 的质量百分含量为30~98%。The sapphire glass etching solution according to claim 1, wherein the hydrochloric acid has a mass percentage of HCl of 15 to 50%, and the phosphoric acid has a mass percentage of H 3 PO 4 of 15 to 50%. The mass percentage of CH 3 COOH in the acetic acid is 30 to 98%.
  3. 如权利要求1或2所述的蓝宝石玻璃蚀刻液，其特征在于，所述蓝宝石玻璃蚀刻液由按以下重量百分含量计的成分组成：The sapphire glass etching solution according to claim 1 or 2, wherein the sapphire glass etching solution is composed of the following components by weight:
    盐酸20%、磷酸10%、醋酸5%、氯化钠2%、纯水63%；或者，Hydrochloric acid 20%, phosphoric acid 10%, acetic acid 5%, sodium chloride 2%, pure water 63%; or,
    盐酸30%、磷酸15%、醋酸10%、氯化钠2%、纯水43%；或者，30% hydrochloric acid, 15% phosphoric acid, 10% acetic acid, 2% sodium chloride, 43% pure water; or,
    盐酸25%、磷酸12%、醋酸8%、氯化钠3%、纯水52%；或者，25% hydrochloric acid, 12% phosphoric acid, 8% acetic acid, 3% sodium chloride, 52% pure water; or,
    盐酸30%、磷酸15%、醋酸10%、氯化钠5%、纯水40%；或者，30% hydrochloric acid, 15% phosphoric acid, 10% acetic acid, 5% sodium chloride, 40% pure water; or,
    盐酸28%、磷酸12%、醋酸6%、氯化钠4%、纯水50%。28% hydrochloric acid, 12% phosphoric acid, 6% acetic acid, 4% sodium chloride, and 50% pure water.
  4. 一种蓝宝石玻璃蚀刻方法，其特征在于，包括：A sapphire glass etching method, comprising:
    按以下重量百分含量计的成分：盐酸20~30%、磷酸10~15%、醋酸5~10%、氯化钠2~5%和纯水40~63%制备蓝宝石玻璃蚀刻液；The sapphire glass etching solution is prepared according to the following components by weight: 20-30% hydrochloric acid, 10-15% phosphoric acid, 5-10% acetic acid, 2~5% sodium chloride and 40-63% pure water;
    采用所述蓝宝石玻璃蚀刻液蚀刻蓝宝石玻璃。The sapphire glass is etched using the sapphire glass etchant.
  5. 如权利要求4所述的蓝宝石玻璃蚀刻方法，其特征在于：所述盐酸中HCl的质量百分含量为15~50%，所述磷酸中H3PO4 的质量百分含量为15~50%，所述醋酸中CH3COOH 的质量百分含量为30~98%。The sapphire glass etching method according to claim 4, wherein the hydrochloric acid has a mass percentage of HCl of 15 to 50%, and the phosphoric acid has a mass percentage of H 3 PO 4 of 15 to 50%. The mass percentage of CH 3 COOH in the acetic acid is 30 to 98%.
  6. 如权利要求4所述的蓝宝石玻璃蚀刻方法，其特征在于，所述蓝宝石玻璃蚀刻液由按以下重量百分含量计的成分组成：The sapphire glass etching method according to claim 4, wherein the sapphire glass etching solution is composed of the following components by weight:
    盐酸20%、磷酸10%、醋酸5%、氯化钠2%、纯水63%；或者，Hydrochloric acid 20%, phosphoric acid 10%, acetic acid 5%, sodium chloride 2%, pure water 63%; or,
    盐酸30%、磷酸15%、醋酸10%、氯化钠2%、纯水43%；或者，30% hydrochloric acid, 15% phosphoric acid, 10% acetic acid, 2% sodium chloride, 43% pure water; or,
    盐酸25%、磷酸12%、醋酸8%、氯化钠3%、纯水52%；或者，25% hydrochloric acid, 12% phosphoric acid, 8% acetic acid, 3% sodium chloride, 52% pure water; or,
    盐酸30%、磷酸15%、醋酸10%、氯化钠5%、纯水40%；或者，30% hydrochloric acid, 15% phosphoric acid, 10% acetic acid, 5% sodium chloride, 40% pure water; or,
    盐酸28%、磷酸12%、醋酸6%、氯化钠4%、纯水50%。28% hydrochloric acid, 12% phosphoric acid, 6% acetic acid, 4% sodium chloride, and 50% pure water.
  7. 如权利要求4～6任一项所述的蓝宝石玻璃蚀刻方法，其特征在于：所述蚀刻蓝宝石玻璃的过程中，所述蓝宝石玻璃蚀刻液的温度为20℃~60℃。The sapphire glass etching method according to any one of claims 4 to 6, wherein in the etching of the sapphire glass, the sapphire glass etching solution has a temperature of 20 ° C to 60 ° C.
  8. 如权利要求7所述的蓝宝石玻璃蚀刻方法，其特征在于：所述蓝宝石玻璃在蚀刻槽内蚀刻，所述蚀刻槽内的温差在5%以内。The sapphire glass etching method according to claim 7, wherein the sapphire glass is etched in an etching bath, and a temperature difference in the etching bath is within 5%.
  9. 如权利要求8所述蓝宝石玻璃蚀刻方法，其特征在于：所述蚀刻槽内的气压为负气压。The sapphire glass etching method according to claim 8, wherein the gas pressure in the etching bath is a negative air pressure.
  10. 如权利要求 4～6任一项所述的蓝宝石玻璃蚀刻方法，其特征在于：所述蚀刻蓝宝石玻璃的蚀刻速率为0.01~0.015mm/min。 As claimed The sapphire glass etching method according to any one of 4 to 6, wherein the etching rate of the etched sapphire glass is 0.01 to 0.015 mm/min.
PCT/CN2014/088466 2014-07-23 2014-10-13 Sapphire glass etching solution and method for etching sapphire glass WO2016011708A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410353840.6A CN104109908B (en) 2014-07-23 2014-07-23 Sapphire glass etching solution and sapphire glass engraving method
CN201410353840.6 2014-07-23

Publications (1)

Publication Number Publication Date
WO2016011708A1 true WO2016011708A1 (en) 2016-01-28

Family

ID=51706890

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/088466 WO2016011708A1 (en) 2014-07-23 2014-10-13 Sapphire glass etching solution and method for etching sapphire glass

Country Status (2)

Country Link
CN (1) CN104109908B (en)
WO (1) WO2016011708A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104651948B (en) * 2015-01-12 2017-05-31 上海应用技术学院 A kind of lithographic method of c surface sapphires
EP3181531A1 (en) * 2015-12-16 2017-06-21 AGC Glass Europe Method for manufacturing a frosted glass sheet
CN107426373A (en) * 2017-09-15 2017-12-01 哈尔滨奥瑞德光电技术有限公司 A kind of Sapphire mobile phone backboard and its processing method
CN107673625A (en) * 2017-11-07 2018-02-09 太仓经济开发区蕴源吉光工艺美术品工作室 Glass etching liquid and glass etching method
CN113735454B (en) * 2021-08-16 2022-12-02 蚌埠高华电子股份有限公司 Low-pressure acid mist etching equipment for liquid crystal glass and automatic control method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2370251B (en) * 2000-12-20 2003-12-03 Lg Philips Lcd Co Ltd Etchant and array substrate having copper lines etched by the etchant
CN101223116A (en) * 2005-07-15 2008-07-16 默克专利有限公司 Printable etching media for silicon dioxide and silicon nitride layers
CN102923963A (en) * 2012-11-15 2013-02-13 杭州格林达化学有限公司 Replenishing liquor for glass thinning etching liquid
US20140038348A1 (en) * 2012-08-03 2014-02-06 Samsung Display Co., Ltd. Etchant composition and manufacturing method for thin film transistor using the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101604666B (en) * 2009-06-19 2011-05-11 中国科学院上海微***与信息技术研究所 Sapphire substrate and polishing method and application thereof
WO2011084887A1 (en) * 2010-01-06 2011-07-14 Avantor Performance Materials, Inc. Chemical compositions for wet chemical modification of sapphire surfaces

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2370251B (en) * 2000-12-20 2003-12-03 Lg Philips Lcd Co Ltd Etchant and array substrate having copper lines etched by the etchant
CN101223116A (en) * 2005-07-15 2008-07-16 默克专利有限公司 Printable etching media for silicon dioxide and silicon nitride layers
US20140038348A1 (en) * 2012-08-03 2014-02-06 Samsung Display Co., Ltd. Etchant composition and manufacturing method for thin film transistor using the same
CN102923963A (en) * 2012-11-15 2013-02-13 杭州格林达化学有限公司 Replenishing liquor for glass thinning etching liquid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIANG, PING ET AL.: "Research on Etching of Pyrex Glass Grooves and Roughness of Their Bottoms", MICROFABRICATION TECHNOLOGY, 15 December 2007 (2007-12-15), pages 63 *
WANG, CHENGYU ET AL.: "The technology state and development of treating glass surface", BUILDING MATERIAL INDUSTRY INFORMATION, 10 November 2003 (2003-11-10), pages 7 *

Also Published As

Publication number Publication date
CN104109908B (en) 2016-08-24
CN104109908A (en) 2014-10-22

Similar Documents

Publication Publication Date Title
WO2016011708A1 (en) Sapphire glass etching solution and method for etching sapphire glass
WO2013170720A1 (en) METHOD FOR PREPARING GRAPHENE-BASED LiFePO4/C COMPOSITE MATERIAL
CN100503450C (en) Method for preparing powder of zirconium oxide in high purity
TWI741116B (en) Silica particle dispersion liquid and its manufacturing method
CN106832961A (en) The preparation method of Graphene thermal conductive silicon rubber cushion
CN108383530A (en) A kind of ZrB2The presoma conversion method preparation process of SiC ceramic composite granule
CN109627050B (en) Quartz crucible inner surface coating and preparation method thereof
CN107032331A (en) A kind of graphene preparation method based on dielectric base
CN105645422B (en) The technique that a kind of liquid phase method prepares spherical super fine zirconium boride powder
CN110937622A (en) Method for preparing 4N gallium oxide from sponge gallium
JPH1017669A (en) Polybenzimidazole solution and its preparation
WO2018108016A1 (en) Graphene modified nano heat-insulating slurry and preparation method therefor
CN109809454B (en) Purification process of colloidal compound
CN114028966A (en) Preparation method of novel nano tin oxide transparent dispersion liquid
JPS59116135A (en) Manufacture of quartz glass
CN113233488B (en) Preparation method of alpha-alumina with narrow primary grain size distribution
CN111115611B (en) Preparation method of high-purity lithium difluorophosphate
CN109852969A (en) A kind of ternary component etching solution of high etch rates
CN109360979B (en) Phosphate radical modified porous titanium dioxide and application thereof in sodium ion battery
CN109627047B (en) Silicon nitride and silicon carbide combined quartz crucible with barium composite coating and preparation method thereof
CN101717244B (en) Composite ceramic carrier for large glass base plate film coating device and preparation method thereof
CN108706631B (en) Preparation method of rectangular flaky monoclinic zirconia
CN112340758A (en) Preparation of high-purity alpha-Al by low-temperature calcination of aluminum ammonium sulfate2O3Method for producing powder
CN115368023B (en) Etching solution, micro-flash AG effect glass and application thereof
CN108863046A (en) The solar energy evacuated effective glass fining agent of one kind and its application

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14897949

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPCN ( EPO FORM 1205A DATED 23-06-2017 )

122 Ep: pct application non-entry in european phase

Ref document number: 14897949

Country of ref document: EP

Kind code of ref document: A1