CN114958302B

CN114958302B - Efficient grinding fluid and preparation method and application thereof

Info

Publication number: CN114958302B
Application number: CN202210580883.2A
Authority: CN
Inventors: 邓中华; 郑连彬
Original assignee: Zhuhai Damons Technology Co ltd
Current assignee: Zhuhai Damons Technology Co ltd
Priority date: 2022-05-26
Filing date: 2022-05-26
Publication date: 2024-06-18
Anticipated expiration: 2042-05-26
Also published as: CN114958302A

Abstract

The invention belongs to the technical field of grinding fluid and provides a high-efficiency grinding fluid and a preparation method and application thereof, wherein a main solvent containing polyalcohol and a cationic compound are adopted as main liquid components of the grinding fluid, the repulsive force effect between grinding materials is improved by means of repulsive force between like charges, the dispersing effect of the grinding materials is improved, the grinding fluid is beneficial to improving the acting time of abrasive particles in a system during operation, the grinding efficiency of the grinding fluid is high, the material removal amount of the grinding fluid is improved by at least 18.78 percent relative to that of a conventional grinding fluid system, the surface roughness can be ensured to be in a nano-scale range of 15-25nm, the pH value of the main solvent is firstly adjusted to be 4-8, then the cationic compound and the grinding materials are sequentially added to prepare the grinding fluid, and the preparation method is simple and convenient and easy to operate, and the prepared grinding fluid is uniform and stable.

Description

Efficient grinding fluid and preparation method and application thereof

Technical Field

The invention relates to the technical field of grinding fluid, in particular to efficient grinding fluid and a preparation method and application thereof.

Background

The sapphire material has hardness which is inferior to that of diamond, has good strength and excellent scratch resistance, and simultaneously has good optical performance, so that the sapphire material has wide application prospect in the electronic consumer market and the wearable equipment market. However, the sapphire material is generally processed through a rough grinding and fine grinding process and a CMP (chemical mechanical polishing) process, and the rough grinding or fine grinding process is used as a pre-process of the CMP process, so that the material removal amount is improved as much as possible while the surface roughness (the surface roughness value Ra is basically required to be greater than 10nm at present) is controlled, so as to improve the working efficiency, improve the productivity and reduce the cost.

Disclosure of Invention

The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the efficient grinding fluid and the preparation method and application thereof, and the grinding fluid provided by the invention can improve the material removal amount, can be applied to rough grinding and fine grinding processes, can improve the grinding efficiency of materials while controlling the surface roughness, improves the material removal amount by at least 18.78% relative to a conventional grinding fluid system, and can ensure the surface roughness to be in a nano-scale range of 15-25 nm.

The first aspect of the present invention provides a highly efficient polishing liquid.

Specifically, the efficient grinding fluid comprises a liquid component and an abrasive;

The liquid component comprises a main solvent and a cationic compound;

The primary solvent comprises a polyol;

the mass of the polyalcohol in the main solvent is more than 70% of the total mass of the grinding fluid;

The mass of the cationic compound is 0.15-15wt% of the total mass of the grinding fluid;

The average grain diameter of the abrasive is more than 1Mic and less than or equal to 100Mic.

The invention adopts the main solvent and the cationic compound as the liquid components of the grinding liquid, wherein the main solvent contains the polyalcohol which is an alkaline system and is prepared together with the grinding materials, and the grain diameter of the grinding materials adopted by the invention reaches the micron level and is difficult to disperse in the system.

Preferably, the cationic compound is one or more of quaternary ammonium salt, tertiary amine salt, ammonium salt, alkali metal salt and alkaline earth metal salt.

More preferably, the cationic compound is a quaternary ammonium salt and/or a tertiary amine salt. The quaternary ammonium salt and the tertiary amine salt are used as a strong cationic compound and can be used as ideal synergists.

Preferably, the quaternary ammonium salt is polyquaternium-10.

Preferably, the mass of the cationic compound is 0.15 to 10wt% of the total mass of the polishing liquid.

Preferably, the mass of the main solvent is 70-99wt% of the total mass of the grinding fluid;

Preferably, the abrasive has an average particle size of 1 to 80Mic.

Preferably, the mass of the polyhydric alcohol in the main solvent is 80% or more of the total mass of the polishing liquid.

Preferably, the main solvent further contains water.

Preferably, the mass of water in the main solvent is 3-30% of the total mass of the grinding fluid.

Preferably, the polyol is one or more of ethylene glycol, glycerol and triethylene glycol.

Preferably, the pH of the polishing liquid is 7-10.

Preferably, the liquid component further comprises one or more of an acid solution, an antifoaming agent, a thickener, a dispersant and a metal corrosion inhibitor.

Preferably, the grinding fluid comprises, in mass percent, based on the total mass of the grinding fluid: 0.1-10wt% of defoamer, 0.1-10wt% of thickener, 0.1-10wt% of dispersant and 0.1-10wt% of metal corrosion inhibitor.

Preferably, the acid solution is one or more of boric acid, dilute hydrochloric acid and acetic acid. The acid solution serves to adjust the pH.

Preferably, the defoamer is a Si-containing, F-type defoamer.

More preferably, the defoamer is simethicone.

Preferably, the thickening agent is one or more of white carbon black, cellulose, polyacrylic acid, polyacrylate, organic bentonite and decadiene cross-linked copolymer.

More preferably, the thickener is hydroxyethyl cellulose.

Preferably, the dispersant is a super dispersant.

Preferably, the metal corrosion inhibitor is one or more of monoethanolamine, triethanolamine, borate, polyphosphate, betaine and benzotriazole derivatives.

Preferably, the mass of the abrasive is 0.2-20wt% of the total mass of the grinding fluid.

Preferably, the abrasive is one or more of diamond agglomerated abrasive, polycrystalline diamond-like abrasive, monocrystalline diamond abrasive, modified diamond abrasive, alumina abrasive, silicon carbide abrasive, silica abrasive, boron carbide abrasive, cerium oxide abrasive, and calcium carbonate abrasive.

The second aspect of the invention provides a method for preparing the efficient grinding fluid.

The invention provides a preparation method for protecting the grinding fluid, which comprises the following steps:

The pH value of the main solvent is adjusted to 4-8 to obtain a first solution, then a cationic compound is added to obtain a second solution, and then an abrasive is added to obtain the grinding fluid.

Preferably, the pH of the main solvent is adjusted using an acid solution.

Preferably, the cationic compound is pre-dissolved in water or an organic solvent to prepare a solution and then added to the first solution.

Preferably, the method further comprises adding a dispersant simultaneously with the cationic compound to obtain a second solution.

Preferably, the method further comprises the steps of adding an antifoaming agent into the second solution, standing to obtain a third solution, adding a thickening agent and a metal corrosion inhibitor to obtain a fourth solution, adding an abrasive, and mixing to obtain the grinding fluid.

Preferably, before the abrasive is added, the method further comprises the step of adding the abrasive into an acetic acid solution, stirring uniformly, and carrying out pretreatment.

Preferably, the mass fraction of the acetic acid solution is 5-8%.

A third aspect of the invention provides for the use of an efficient grinding fluid.

The invention protects the application of the grinding fluid in material processing.

Preferably, the material is a brittle material.

More preferably, the material is silicon carbide, sapphire, ceramic material.

Preferably, the material is processed to produce a semiconductor component.

Preferably, the polishing liquid is used in a rough grinding or fine grinding process in the preparation of semiconductor elements.

Preferably, the polishing liquid is a polishing liquid for a double-sided non-copper disk polishing machine or a single-sided polishing machine.

Compared with the prior art, the invention has the following beneficial effects:

(1) According to the invention, the main solvent containing polyol and the cationic compound are adopted as main liquid components of the grinding fluid, and as the cationic compound provides strong positive charge static force and has repulsive force with the grinding material with positive charge, the cationic compound can be used as a synergistic agent to increase the density of charges, improve repulsive force among the grinding materials, improve the dispersing effect of the grinding materials, and can achieve the effect of improving repulsive force among the grinding materials by means of repulsive force among like charges, when the grinding fluid is in operation, the grinding particles are ensured not to be settled as much as possible, the action time of the grinding particles in the system is prolonged, the grinding efficiency is improved, the material removal amount of the grinding fluid is improved by at least 18.78% relative to that of a conventional grinding fluid system, and the surface roughness is ensured to be in a nano-scale range of 15-25 nm;

(2) The invention firstly adjusts the pH value of the main solvent to 4-8, then sequentially adds the cationic compound and the abrasive, and because the main solvent contains the polyalcohol, the pH value of the main solvent is firstly adjusted, and then the cationic compound is added to ensure the stability of the whole system, avoid the system failure caused by hydrogen generation, simultaneously, the cationic compound is conveniently and further introduced, and the uniform and stable grinding fluid can be prepared by adding the abrasive after the cationic compound is added.

Detailed Description

In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.

The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.

The raw materials adopted in the examples and comparative examples of the present invention are as follows:

And (3) grinding materials:

diamond micropowder A (standard type) with average particle diameter of 2Mic;

diamond micropowder B (porous type) with average particle size of 2Mic;

Diamond micropowder C (super-hard type) with average particle diameter of 2Mic;

Diamond micropowder D (standard type) with an average particle size of 0.75Mic;

The diamond micro powder A-D is diamond agglomerated micro powder produced by the Martensitic Dai Mengsi technology Co., ltd.:

The boron carbide micro powder is purchased externally and has an average particle size of 10Mic.

Polyol: triethylene glycol, triple well.

Cationic compound: polyquaternium-10, dow.

Defoaming agent: simethicone and daokanning.

And (3) a thickening agent: hydroxyethylcellulose (HEC), dow.

Dispersing agent: hyperdispersant, basf XL40.

Metal corrosion inhibitors: triethanolamine, basf.

Acid solution: acetic acid with mass fraction of 5%.

Example 1

An efficient grinding fluid comprises a liquid component and an abrasive, wherein the liquid component comprises a main solvent and a cationic compound, the main solvent comprises a polyalcohol, and the pH of the grinding fluid is 8-9.

The mass percentages of the components based on the total mass of the grinding fluid are shown in table 1.

Examples 2 to 12 and comparative examples 1 to 10

The components and amounts of the components of examples 2-12 and comparative examples 1-10 are shown in Table 1.

Table 1 the components of each of the examples and comparative examples and the amounts thereof (unit: wt% based on the total mass of the polishing liquid)

The preparation method of the grinding fluid of each embodiment comprises the following steps:

(1) Adding an acid solution into the main solvent, and regulating the pH value to 7-8 to obtain a first solution;

(2) The quaternary ammonium salt is pre-dissolved by water to prepare a solution, and then the pre-dissolved quaternary ammonium salt and the dispersing agent are added into the first solution and uniformly stirred to obtain a second solution;

(3) Adding an antifoaming agent into the second solution, uniformly stirring, and standing for 24 hours to obtain a third solution;

(4) Adding a thickener and a metal corrosion inhibitor into the third solution, and uniformly stirring to obtain a fourth solution;

(5) Firstly, uniformly stirring the abrasive with an acetic acid solution with the mass fraction of 5%, carrying out pretreatment, then adding the pretreated abrasive into a fourth solution, and uniformly stirring to obtain the grinding fluid.

Application example 1

The polishing liquids prepared in the examples and comparative examples described above were applied to the rough grinding process of the sapphire material processing process. The equipment used in the related experiment is a ZYP230 type rotary swinging single-sided grinder, a lower disc is stuck with a grinding sheet, a test workpiece is stuck on an upper disc, grinding liquid is pumped to a working disc surface by a peristaltic pump, and continuous stirring of the grinding liquid is ensured during the test.

1. Test method

Test equipment: ZYP230 type rotary swing single-sided grinder.

The rest used equipment: 2.2KW high-speed dispersing machine; BWS-6-SN balance with 0.1g precision; an HY-602 balance with the precision of 10 g; a PC-905A pH meter with the precision of 0.01, wherein a weighing instrument is METTLER TOLEDO AB204S analytical balance; MITUTOYO SJ210 roughness tester with 0.001um precision; the grinding skin is made of resin material with a three-dimensional structure of model SPHU manufactured by Zhu-hai Dai Mengsi technology Co., ltd.

Pressure in the weight test: 6KG; millstone revolution: 75RPM (briquetting RPM: 60RPM, swing 10 mm); flow rate of polishing liquid: 4mL/min; grinding time: 30mins; materials: c, sapphire with diameter of 25mm and 3 pieces/mill.

Pressure in light pressure test: 2.4KG; millstone revolution: 50RPM (briquetting RPM: 50RPM, swing 10 mm); flow rate of polishing liquid: 3mL/min; grinding time: 40mins; materials: c, sapphire with diameter of 25mm and 3 pieces/mill.

The testing method comprises the following steps: before the experiment is carried out, the sample is coarsely ground by adopting an SRD-20 diamond grinding pad manufactured by the Pinctada Dai Mengsi technology Co., ltd., the single-sided removal amount is 80-100Mic, so that the surface condition of a processed workpiece before each experiment is basically consistent, and the Ra after coarse grinding (before fine grinding): 0.35-0.40Mic.

The experimental removal amount is calculated by adopting a weight reduction method, namely: before each experiment, cleaning and drying a processed workpiece, and weighing by an analytical balance to obtain the weight before grinding; after the experiment, the processed workpiece is cleaned again, dried and weighed by an analytical balance to obtain the ground weight.

Since the sapphire sample to be tested is replaced during the test, the dimensions are not completely uniform, and thus, in order to reduce errors, a reference is set each time the sapphire sample to be tested is replaced. In the present invention, the polishing efficiency of the polishing liquid is expressed in terms of the amount of material removed and the percentage increase relative to the reference, and the higher the amount of material removed and the percentage increase relative to the reference, the higher the polishing efficiency of the polishing liquid.

Material removal (weight reduction) =pre-mill weight-post-mill weight, units are calculated in g.

Percent improvement = weight reduction of test sample/weight reduction of baseline x 100%.

2. Test results

The Ra after finish grinding of all samples was in the 15-25nm region and the surface roughness was in the nanometer range, as measured by a MITUTOYO SJ210 roughness meter.

TABLE 2 influence of different proportions of Quaternary ammonium salts on grinding efficiency in the weight test

As is clear from the results of Table 2, in the heavy-load test, the polishing solutions of examples 1 to 3 of the present invention, to which the quaternary ammonium salt was added, had high polishing efficiency as compared with the polishing solution of comparative example 1, which did not contain the quaternary ammonium salt.

TABLE 3 influence of different proportions of Quaternary ammonium salts on grinding efficiency in light pressure test

As is clear from the results of Table 3, in the light pressure test, the polishing solutions of examples 1 to 3 of the present invention, in which the quaternary ammonium salt was added, had high polishing efficiency as compared with the polishing solution of comparative example 1, in which the quaternary ammonium salt was not contained.

TABLE 4 influence of different proportions of thickeners on grinding efficiency in the weight test

As is clear from the results of Table 4, the polishing efficiency of the polishing slurries of examples 3 to 6 of the present invention gradually increased with the increase in the amount of the thickener in the weight test.

TABLE 5 influence of different proportions of thickeners on grinding efficiency in light pressure test

As is clear from the results of Table 5, the polishing efficiency of the polishing slurries of examples 3 to 5 of the present invention gradually increased with the increase in the amount of the thickener in the light pressure test. When 0.2% of thickener is added in example 6, the improvement percentage is slightly reduced, because the viscosity is too high under the light pressure working condition, the fluidity of the grinding fluid is reduced, the grinding material is difficult to well enter the disc surface, the actual grinding quantity of the disc surface is small, and the cutting force is reduced, so that the grinding effect of the grinding fluid added with 1% of quaternary ammonium salt is optimal in the light pressure test.

TABLE 6 influence of different types of abrasives on grinding efficiency in the stress test

As can be seen from the results of table 6, in the heavy pressure test, the polishing efficiency of example 7 of the present invention was higher than that of comparative example 2, in which the quaternary ammonium salt and the thickener were not added, and the difference between example 7 and example 6 was that different types of abrasives were used, and the polishing efficiency was better, indicating that the polishing liquid system of the present invention was suitable for different types of abrasives.

Table 7 effect of different types of abrasives on grinding efficiency in light pressure test

As can be seen from the results of table 7, in the light pressure test, the polishing efficiency of example 8 of the present invention was higher than that of comparative example 3, in which the quaternary ammonium salt and the thickener were not added, and the difference between example 8 and example 5 was that different kinds of abrasives were used, and the polishing efficiency was better, indicating that the polishing liquid system of the present invention was suitable for different types of abrasive grains.

Table 8 effect of different types of abrasives on grinding efficiency in the stress test

As can be seen from the results of table 8, in the heavy pressure test, the polishing efficiency of example 9 of the present invention was higher than that of comparative example 3, in which the quaternary ammonium salt and the thickener were not added, and the difference between example 9 and example 6 was that different kinds of abrasives were used, and good polishing efficiency was obtained, indicating that the polishing liquid system of the present invention was suitable for different types of abrasive grains.

Table 9 effect of different types of abrasives on grinding efficiency in light pressure test

As can be seen from the results of table 9, in the light pressure test, the polishing efficiency of example 10 of the present invention was higher than that of comparative example 4, in which the quaternary ammonium salt and the thickener were not added, and the difference between example 10 and example 5 was that different kinds of abrasives were used, and the polishing efficiency was better, indicating that the polishing liquid system of the present invention was suitable for different types of abrasive grains.

Application example 2

The polishing liquids prepared in the examples and comparative examples described above were applied to the rough grinding process of the sapphire material processing process. The equipment used in the test of tables 10-12 below was a SHJ6S-5L double-sided grinder, the upper and lower plates were bonded with a skin, the test piece was secured to the working surface with a free wheel, the slurry was pumped to the working surface with peristaltic pumps, and during the test, the slurry was allowed to continue stirring.

The rest used equipment: 2.2KW high-speed dispersing machine; BWS-6-SN balance with 0.1g precision; an HY-602 balance with the precision of 10 g; the PC-905A pH meter with the precision of 0.01 is provided, the weighing instrument is METTLER TOLEDO AB204S analytical balance, and the MITUTOYO SJ210 roughness tester with the precision of 0.001 um.

Test conditions: 16KG pressure, upper/lower disc revolution: 9/30RPM, flow: 3ml/min, milling time: 50min; sapphire workpiece: c25 mm 15 pcs/disc.

The testing method comprises the following steps: before the experiment is carried out, the sample is coarsely ground by adopting an SRD-20 diamond grinding pad manufactured by Martensitic Dai Mengsi technology Co., ltd., the double-sided removal amount is 100-150Mic, so that the surface condition of a processed workpiece before each experiment is basically consistent, and Ra is ensured after coarse grinding (before fine grinding): 0.35-0.40Mic;

the experimental removal amount is calculated by adopting a weight reduction method, namely: before each experiment, cleaning and drying a processed workpiece, and weighing by an analytical balance to obtain the weight before grinding; after the experiment, the processed workpiece is cleaned again, dried and weighed by an analytical balance to obtain the weight after grinding.

The grinding skin is made of resin material with a three-dimensional structure of model SPHU manufactured by Zhu-hai Dai Mengsi technology Co., ltd.

TABLE 10 Effect of different amounts of Quaternary ammonium salt on grinding efficiency

As is clear from the results of Table 10, the polishing slurry of comparative example 7 is different from that of example 11 in that the mass percentage of the quaternary ammonium salt of comparative example 7 is reduced to 0.1%, and the weight reduction of example 11 of the present invention is improved by nearly 50% as compared with that of comparative example 7, because the abrasive grain size used in the present invention reaches the micrometer scale, the dispersion effect is poor, and if the quaternary ammonium salt concentration is too low, the electrostatic force to the abrasive is too small, the effect is insignificant, resulting in a decrease in the polishing efficiency of the polishing slurry.

TABLE 11 influence of different amounts of water on grinding efficiency

As is clear from the results of Table 11, the polishing slurry of comparative example 9 was different from that of example 12 in that the amount of triethylene glycol in the polishing slurry was reduced, and the polishing efficiency of comparative example 9 was lowered due to the fact that the polyquaternium-10 was insoluble in water, and therefore, the addition of water resulted in a decrease in the actual cationic charge density, a decrease in the repulsive force between diamond fine powders, easier sedimentation, and a decrease in the effective time of diamond fine powders at the time of operation, thereby resulting in a decrease in the polishing efficiency.

TABLE 12 influence of abrasives of different particle sizes on grinding efficiency

As is clear from the results of table 12, the polishing liquid of example 11 is different from comparative example 10 in that the difference in the particle size of the diamond fine powder in the polishing liquid, the reduction in the particle size of the diamond fine powder of comparative example 10 to 0.75Mic, resulted in a great decrease in the polishing efficiency of comparative example 10, and although the surface roughness of comparative example 10 was still on the nano scale, the polishing efficiency was not improved because the particle size of diamond itself was too small, which suggests that in the finish grinding process, it was necessary to find a balance between the polishing efficiency and the surface quality of the work piece after processing, so that the polishing efficiency could be improved while the control of the surface roughness was ensured to the nano scale.

Claims

1. The grinding liquid for the grinding skin of the resin material with the three-dimensional structure is characterized by comprising a liquid component and an abrasive;

The grinding fluid is characterized by further comprising the following components in percentage by mass based on the total mass of the grinding fluid: 0.1-10wt% of defoamer, 0.1-0.2wt% of thickener, 0.1-10wt% of dispersant, 0.1-10wt% of metal corrosion inhibitor;

The liquid component comprises a main solvent and a cationic compound;

The primary solvent comprises a polyol;

The mass of the polyalcohol in the main solvent is more than 80% of the total mass of the grinding fluid;

the cationic compound is quaternary ammonium salt and/or tertiary amine salt;

the mass of the cationic compound is 1wt% of the total mass of the grinding fluid;

The mass of the abrasive is 1wt% of the total mass of the grinding fluid;

The average grain diameter of the abrasive is 2Mic;

the pH value of the grinding fluid is 7-10;

the grinding skin of the resin material with the three-dimensional structure is the grinding skin of the resin material with the three-dimensional structure, which is manufactured by the Pinctada Dai Mengsi technology Co., ltd, and has the model number SPHU;

The preparation method of the grinding fluid comprises the following steps:

The pH value of the main solvent is adjusted to 4-8 to obtain a first solution, then a cationic compound is added, a dispersing agent is added at the same time to obtain a second solution, a defoaming agent is added, standing is carried out to obtain a third solution, a thickening agent and a metal corrosion inhibitor are added to obtain a fourth solution, an abrasive is added, and the grinding fluid is obtained after mixing.

2. The polishing slurry for a polishing pad of a resin material having a three-dimensional structure according to claim 1, wherein the abrasive is one or more of a diamond agglomerated abrasive, a modified diamond abrasive, an alumina abrasive, a silicon carbide abrasive, a silica abrasive, a boron carbide abrasive, a cerium oxide abrasive, and a calcium carbonate abrasive.

3. The method for producing a polishing slurry for polishing a resin material having a three-dimensional structure according to claim 1 or 2, comprising the steps of:

4. Use of the polishing liquid for polishing a resin material having a three-dimensional structure according to claim 1 or 2 in material processing.