CN113603355A - Mold release agent for crystallization process of ultrathin glass and preparation method thereof - Google Patents
Mold release agent for crystallization process of ultrathin glass and preparation method thereof Download PDFInfo
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
- C03B40/02—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it by lubrication; Use of materials as release or lubricating compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
Abstract
The invention discloses a mold release agent for an ultrathin glass crystallization process, which consists of 12-60 wt% of a mixture of submicron hexagonal boron nitride and submicron beta silicon carbide, 1-2 wt% of a wetting dispersant, 0.01-0.05 wt% of an antifoaming agent, 0.4-1.2 wt% of a surface auxiliary agent, 20-80 wt% of silica sol and the balance of softened water. The release agent provided by the invention has the advantages of high temperature resistance, stable chemical performance, good thermal conductivity and excellent release effect, the preparation method of the release agent is simple, no harmful substance is volatilized in the processing process, and the influence on the environment is small.
Description
Technical Field
The invention belongs to the field of a ceramization method and equipment for a glass sheet, and particularly relates to a release agent for an ultrathin glass crystallization process and a preparation method thereof.
Background
With the rapid development of flat panel display technology, the demand of ultra-thin glass in the world market is huge, and in the past few years, the demand of ultra-thin glass in the international market is increasing at a rate of 20% per year. The demand of ultra-thin glass in China is increasing day by day, and according to estimation, the annual demand of the ultra-thin float glass in China is about 8000 ten thousand meters2And increases at a rate of 15% per year. In addition to being used for flexible display substrate materials (such as apple and curved mobile phones pushed by samsung), the ultrathin glass is expected to be used in the fields of OLED lighting, adapter plates for LSI, capacitors, lithium ion rechargeable batteries and the like. Due to the characteristics of glass, such as high gas tightness, thermal stability, light transmittance, corrosion resistance, etc., ultra-thin glass may also gradually be involved in some application fields of organic polymers and metals.
Nucleation and crystal growth of glass-ceramics are usually at the glass transition temperature TgAbove and below the melting point of the main crystal phase. Generally corresponding to 1010～1012The nucleation is performed by keeping the temperature of the viscosity of Pa.s for a certain time, so that a certain number of crystal nuclei with uniform distribution are formed in the mother glass. For glasses that are very susceptible to crystallization (e.g., systems with lower melt viscosity and higher alkali metal oxide content), the nucleation stage can also be omitted and the glasses can be heated directly to the crystal growth temperature, since these glasses can complete nucleation during the temperature rise process, resulting in a large number of nuclei. The crystal growth temperature is generally about 100 to 200 ℃ higher than the nucleation temperature.
According to the literature, the highest thermal conductivity of the silicon carbide single crystal at room temperature is 490W/(M.K), and the highest thermal conductivity of the silicon carbide ceramic at room temperature is 270W/(M.K). At temperatures above about 800K, the thermal conductivities of the silicon carbide single crystal and the silicon carbide ceramic are substantially the same, and the phonon interaction dominates the thermal conductivity mechanism. This is caused by the fact that the difference in thermal conductivity between silicon carbide ceramic and single crystal is large at low temperature, the scattering effect between phonons is reduced with the decrease in temperature, and the scattering of phonons by defects and grain boundaries is increased under the action of the thermal conductivity mechanism.
In the field of the present ultra-thin glass, represented by Corning, Schott of Germany, AGC of Japan, and building material information display materials Limited in the Union of China, the thickness of the glass can be reduced to below 0.2mm, and the glass can be produced in batch. However, in the field of ultra-thin microcrystalline glass, no enterprises can be produced in the world at present, and the main reason is that the ultra-thin microcrystalline glass is too thin to be subjected to crystallization heat treatment, and if the heat treatment is not proper, the ultra-thin glass generates various defects such as large warpage (>700 μm) or devitrification due to too large crystal growth.
Disclosure of Invention
Aiming at the problems in the development process of ultrathin glass ceramics, the invention provides a release agent for the crystallization process of ultrathin glass.
In order to solve the technical problems, the invention adopts the following technical scheme:
the mold release agent for the crystallization process of the ultrathin glass comprises 12-60 wt% of a mixture of submicron hexagonal boron nitride and submicron beta silicon carbide, 1-2 wt% of a wetting dispersant, 0.01-0.05 wt% of an antifoaming agent, 0.4-1.2 wt% of a surface auxiliary agent, 20-80 wt% of silica sol and the balance of softened water.
Further, the release agent also contains 0-2 wt% of a PH regulator.
The mixture of the submicron hexagonal boron nitride and the submicron beta silicon carbide consists of the submicron hexagonal boron nitride and the submicron beta silicon carbide in a mass ratio of 1: 2; the particle size distribution of the mixture of the submicron hexagonal boron nitride and the submicron beta silicon carbide is as follows: 50-60 Vol% of submicron particles with an average particle size of 0.5-0.8 μm, 30-40 Vol% of submicron particles with an average particle size of 0.3-0.5 μm, and 10-20 Vol% of submicron particles with an average particle size of 0.1-0.3 μm.
The point defect of the submicron-scale beta silicon carbide is less than or equal to 0.3 percent.
The viscosity of the release agent is 10-2100 cP.
The solid content of a wet film prepared from the release agent is 30-60 wt%, and the PH is 6-8; the thermal conductivity coefficient of a dry film prepared from the release agent is 30-90W (M.K).
The wetting dispersant is one or more of salt solution of unsaturated polyamine amide and/or acidic polyester, the defoaming agent is polydimethylsiloxane, the surface auxiliary agent is polysiloxane and/or polyacrylate, and SiO in the silica sol2The content of (B) is 30 wt%.
The pH regulator is one or more of citric acid, sorbic acid, sodium bicarbonate or disodium hydrogen phosphate.
A method for preparing a mold release agent for an ultra-thin glass crystallization process, characterized by comprising the steps of:
the method comprises the following steps: uniformly mixing 4-20 wt%, 8-40 wt%, 20-80 wt% of submicron hexagonal boron nitride, submicron beta silicon carbide and silica sol in softened water, and gradually adding 1-2 wt% of wetting dispersant in the stirring process until the solution is uniform and off-white;
step two: carrying out ultrasonic oscillation deflocculation on the solution obtained in the first step for 4-5 hours in a water bath, setting the ultrasonic power of an ultrasonic cleaning machine to be 400-500W, and setting the temperature of the ultrasonic cleaning machine to be 50-80 ℃; flocculation is easily caused in the step, so that ultrasonic vibration deflocculation is adopted while the surface wetting agent is added, rather than the traditional stirring;
step three: slowly stirring the uniform solution obtained in the second step for 2-3 hours after 0.01-0.05 wt% of defoaming agent is added, adding 0-2 wt% of PH regulator in the stirring process, and regulating the PH of the solution to be neutral;
step four: and (3) adding 0.4-1.2 wt% of surface auxiliary agent into the solution obtained in the step three, continuously stirring at a low speed for 0.5-1 h, and fully reacting to obtain the release agent for the crystallization process of the ultrathin glass.
The wetting dispersant in the step one is one or more of salt solution of unsaturated polyamine amide and/or acidic polyester, SiO in silica sol2The content of (A) is 30%; the defoaming agent in the third step is polydimethylsiloxane; the surface auxiliary agent in the fourth step is polysiloxane and/or polyacrylate。
A use method of a release agent for an ultrathin glass crystallization process comprises the steps of firstly spraying the release agent on the surface of a glass substrate in a spraying mode for 2 times, wherein each time of spraying is carried out along different directions to ensure that no spray leakage exists, the interval between each time of spraying is 1 minute, the next time of spraying is carried out after the previous time of spraying, drying and curing, then stacking the glass substrates in an oven at 120 ℃, and finally drying the glass substrates at 80-105 ℃.
The thickness of the release agent (wet film) on the surface of the glass substrate is 6-10 μm.
The thickness of the release agent (dry film) on the surface of the glass substrate is 2-5 mu m.
The thickness of the ultrathin glass substrate is 0.12-1.0 mm.
The pressure of the spray gun used by the invention is set to be 0.2-0.3 MPa, and the vertical distance between the spray head and the ultrathin glass substrate is 10-15 cm.
The ultrathin glass substrate can be stacked to 30 layers at most.
The maximum warping of the ultra-thin glass substrate after crystallization is less than 100 mu m.
Boron nitride is a compound which is formed by stacking hexagonal networks and is similar to a graphite structure, wherein the boron nitride has corrosion resistance and good electrical insulation property; the heat resistance of the material reaches 900 ℃ under an oxygen environment and is more than one time of that of graphite, and the heat resistance of the material reaches 2800 ℃ under a non-oxidation-reduction atmosphere, and the material has extremely high heat conductivity which is about ten times more than that of a quartz material, has a low friction coefficient (0.16), cannot be increased at high temperature, and also has excellent lubricity and high-temperature stability. Therefore, boron nitride has great advantages and development potential as a glass mold release agent.
The highest thermal conductivity of the silicon carbide single crystal at room temperature is 490W/(M.K), and the highest thermal conductivity of the silicon carbide ceramic at room temperature is 270W/(m.K). At temperatures above about 800K, the thermal conductivities of the silicon carbide single crystal and the silicon carbide ceramic are substantially the same, and the phonon interaction dominates the thermal conductivity mechanism. This is caused by the fact that the difference in thermal conductivity between silicon carbide ceramic and single crystal is large at low temperature, the scattering effect between phonons is reduced with the decrease in temperature, and the scattering of phonons by defects and grain boundaries is increased under the action of the thermal conductivity mechanism.
Silica sol is a colloidal solution of silica colloidal particles uniformly dispersed in water, and the colloidal particles are very small and therefore have a considerable surface area. In addition, the colloidal particles are colorless and transparent, and do not affect the natural color of the covering. Meanwhile, the water-based paint has low viscosity and can be penetrated in places where water can penetrate. Therefore, when mixed with other substances, the dispersion and the permeability are very good. The silica sol does not need a curing agent, can be firmly adsorbed on the surface of a solid and forms a firm film, and the film forming temperature is low, so that when the silica sol is heated to 110 ℃, free water in the silica sol is completely lost, and a solid gel can be formed by drying or sintering, so that the silica sol has certain durability. The silica sol has good chemical uniformity, high purity, fine particles, high activity and low cost of raw materials, and is an inorganic high molecular compound with an anion framework and has special reaction capacity and adsorption effect on aluminum ions.
On the one hand, the beta silicon carbide is in a cubic structure, the size of the beta silicon carbide is larger than that of silicon dioxide, and the silicon dioxide can be adsorbed on the beta silicon carbide, so that the phenomenon that the nano silicon dioxide in silica sol forms a non-spherical structure is avoided or reduced, the viscosity of the release agent is avoided being reduced, and the problem that the release agent cannot be effectively bonded is avoided; on the other hand, the heat conductivity coefficient can be enhanced by adding the beta silicon carbide, heat can be effectively transferred to the stacked inner glass, the number of stacked layers of the glass substrate can be increased, the production efficiency is improved, the generation of glass surface warping can be effectively reduced, and the quality of the ultrathin glass after heat treatment is improved.
The release agent provided by the invention has the advantages of high temperature resistance, stable chemical performance, good thermal conductivity and excellent release effect, the preparation method of the release agent is simple, no harmful substance is volatilized in the processing process, and the influence on the environment is small.
Drawings
FIG. 1 is a schematic diagram of the construction of an ultra-thin glass stack according to examples 1-18.
101-a release agent coating; 102-ultra-thin glass substrate.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The mold release agent for the crystallization process of the ultrathin glass has the following raw materials in proportion:
5 wt% of submicron hexagonal boron nitride (h-BN), 40 wt% of submicron beta silicon carbide (beta-SiC), 2 wt% of wetting dispersant (unsaturated polyamine amide), 0.02 wt% of defoaming agent (polydimethylsiloxane), 1.0 wt% of surface additive (polysiloxane), 40 wt% of silica sol, 1 wt% of PH regulator (citric acid) and the balance of softened water.
The mold release agent for the crystallization process of the ultrathin glass is prepared by the following steps:
the method comprises the following steps: uniformly mixing submicron hexagonal boron nitride, submicron beta silicon carbide and silica sol in softened water, and gradually adding a wetting dispersant (unsaturated polyamine amide) in the stirring process until the solution is uniform and grey white;
step two: carrying out ultrasonic oscillation deflocculation on the solution obtained in the first step for 5 hours in a water bath, wherein the ultrasonic power of an ultrasonic cleaning machine is set to be 500W, and the temperature of the ultrasonic cleaning machine is set to be 80 ℃;
step three: slowly stirring the uniform solution obtained in the second step for 3 hours after adding a defoaming agent (polydimethylsiloxane), adding a pH regulator (citric acid) in the stirring process, and regulating the pH of the solution to be neutral;
step four: and (3) adding the surface auxiliary agent into the solution obtained in the third step, continuously stirring at a low speed for 1h, and fully reacting to obtain the release agent for the crystallization process of the ultrathin glass.
The application method of the mold release agent for the crystallization process of the ultrathin glass in the embodiment comprises the following steps:
firstly, spraying a release agent on the surface of the ultrathin glass substrate in a spraying mode for 2 times, wherein each time is carried out along different directions to ensure that no spray leakage exists, the interval between each time of spraying is 1 minute, the next time of spraying is carried out after the previous time of spraying, drying and curing, then the ultrathin glass substrates are stacked in a 120 ℃ oven in sequence, and finally the ultrathin glass substrates are dried at 105 ℃.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1273K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.12mm, and the heat treatment temperature is 1273K.
The procedure for preparing and using the release agents used in examples 2 to 18 was the same as in example 1.
Example 2
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 1.
The mold release performance test of this example was: spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1073K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.5mm, and the heat treatment temperature is 1273K.
Example 3
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 1.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 873K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 1.0mm, and the heat treatment temperature is 1273K.
Example 4
The mold release agent for the crystallization process of the ultrathin glass has the following raw materials in proportion:
15 wt% of submicron hexagonal boron nitride (h-BN), 30 wt% of submicron beta silicon carbide (beta-SiC), 2 wt% of wetting dispersant (unsaturated polyamine amide), 0.02 wt% of defoaming agent (polydimethylsiloxane), 1.0 wt% of surface additive (polysiloxane), 40 wt% of silica sol, 1 wt% of pH regulator (citric acid) and the balance of softened water.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1273K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.12mm, and the heat treatment temperature is 1273K.
Example 5
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 4.
The mold release performance test of this example was: spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1073K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.5mm, and the heat treatment temperature is 1273K.
Example 6
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 4.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 873K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 1.0mm, and the heat treatment temperature is 1273K.
Example 7
The mold release agent for the crystallization process of the ultrathin glass has the following raw materials in proportion:
20 wt% of submicron hexagonal boron nitride (h-BN), 25 wt% of submicron beta silicon carbide (beta-SiC), 2 wt% of wetting dispersant (unsaturated polyamine amide), 0.02 wt% of defoaming agent (polydimethylsiloxane), 1.0 wt% of surface additive (polysiloxane), 40 wt% of silica sol, 1 wt% of pH regulator (citric acid) and the balance of softened water.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1273K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.12mm, and the heat treatment temperature is 1273K.
Example 8
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that of the embodiment 7.
The mold release performance test of this example was: spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1073K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.5mm, and the heat treatment temperature is 1273K.
Example 9
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 4.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 873K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 1.0mm, and the heat treatment temperature is 1273K.
Example 10
The mold release agent for the crystallization process of the ultrathin glass has the following raw materials in proportion:
15 wt% of submicron hexagonal boron nitride (h-BN), 30 wt% of submicron beta silicon carbide (beta-SiC), 2 wt% of wetting dispersant (unsaturated polyamine amide), 0.02 wt% of defoaming agent (polydimethylsiloxane), 1.0 wt% of surface additive (polysiloxane), 20 wt% of silica sol, 0.5 wt% of pH regulator (citric acid) and the balance of softened water.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1273K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.12mm, and the heat treatment temperature is 1273K.
Example 11
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that of the embodiment 10.
The mold release performance test of this example was: spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1073K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.5mm, and the heat treatment temperature is 1273K.
Example 12
The raw material proportion, the preparation method and the using method of the release agent for the crystallization process of the ultrathin glass in the embodiment are the same as those in the embodiment 10.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 873K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 1.0mm, and the heat treatment temperature is 1273K.
Example 13
The mold release agent for the crystallization process of the ultrathin glass has the following raw materials in proportion:
8 wt% of submicron hexagonal boron nitride (h-BN), 15 wt% of submicron beta silicon carbide (beta-SiC), 2 wt% of wetting dispersant (unsaturated polyamine amide), 0.02 wt% of defoaming agent (polydimethylsiloxane), 1.0 wt% of surface additive (polysiloxane), 60 wt% of silica sol, 1.5 wt% of pH regulator (citric acid) and the balance of softened water.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1273K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.12mm, and the heat treatment temperature is 1273K.
Example 14
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that of the embodiment 13.
The mold release performance test of this example was: spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1073K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.5mm, and the heat treatment temperature is 1273K.
Example 15
The raw material ratio, the preparation method and the using method of the release agent for the crystallization process of the ultrathin glass in the embodiment are the same as those in the embodiment 13.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 873K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 1.0mm, and the heat treatment temperature is 1273K.
Example 16
The mold release agent for the crystallization process of the ultrathin glass has the following raw materials in proportion:
4 wt% of submicron hexagonal boron nitride (h-BN), 8 wt% of submicron beta silicon carbide (beta-SiC), 2 wt% of wetting dispersant (unsaturated polyamine amide), 0.02 wt% of defoaming agent (polydimethylsiloxane), 1.0 wt% of surface additive (polysiloxane), 80 wt% of silica sol, 2 wt% of PH regulator (citric acid) and the balance of softened water.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1273K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.12mm, and the heat treatment temperature is 1273K.
Example 17
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 16.
The mold release performance test of this example was: spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 1073K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 0.5mm, and the heat treatment temperature is 1273K.
Example 18
The raw material ratio of the release agent for the crystallization process of the ultrathin glass in the embodiment is the same as that in the embodiment 16.
The mold release performance test of this example was: and spraying a release agent on the surface of the ultrathin glass, wherein the heat treatment temperature is 873K.
The crystallization experiment of this example was: the thickness of the adopted ultrathin glass is 1.0mm, and the heat treatment temperature is 1273K.
The adjuvants employed in the above examples (wetting and dispersing agent, defoamer, surface adjuvant) were from Pickering adjuvant (Shanghai) Co., Ltd.
The ultra-thin glasses used in the experiments of the above examples were all from Union-Tibet building materials information display materials, Inc., and have a size of 8X 8 cm.
The lance used in the above example was LPH-50 manufactured by Nippon Denshoku Kogyo.
The dispersibility, leveling property, thickness, leveling property, surface tension, average particle diameter and viscosity of the release agents (wet films) in examples 1 to 18 above were characterized, and the results are shown in table 1 below.
TABLE 1
The thickness, viscosity and thermal conductivity at different temperatures of the release agent (dry film) in examples 1 to 18 above were characterized, and the results are shown in table 2 below.
TABLE 2
The number of stacked layers, mold release properties, uniformity, and warpage of the ultrathin glass substrates in examples 1 to 18 above were characterized, and the results are shown in table 3 below.
TABLE 3
As can be seen from the above tables 1, 2 and 3, the release agent provided by the invention has the advantages of high temperature resistance, stable chemical performance, strong adhesive force, good thermal conductivity and excellent release effect, and the h-BN and the beta-SiC in the invention adopt a gradient distribution form to select the particle size, so that a closest packing structure can be formed on the surface of a glass substrate, and the release agent is more suitable for industrial production and can be used in the future production field of ultrathin glass ceramics.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The mold release agent for the crystallization process of the ultrathin glass is characterized by comprising 12-60 wt% of a mixture of submicron hexagonal boron nitride and submicron beta silicon carbide, 1-2 wt% of a wetting dispersant, 0.01-0.05 wt% of an antifoaming agent, 0.4-1.2 wt% of a surface auxiliary agent, 20-80 wt% of silica sol and the balance of softened water.
2. The mold release agent for crystallization of ultra-thin glass as claimed in claim 1, further comprising 0 to 2 wt% of a pH adjusting agent.
3. The mold release agent for crystallization of ultra-thin glass according to claim 1 or 2, characterized in that the mixture of submicron-sized hexagonal boron nitride and submicron-sized beta-silicon carbide is composed of submicron-sized hexagonal boron nitride and submicron-sized beta-silicon carbide in a mass ratio of 1: 2.
4. The mold release agent for ultra-thin glass crystallization process according to claim 3, characterized in that the particle size distribution of the mixture of submicron hexagonal boron nitride and submicron beta silicon carbide is: 50-60 Vol% of submicron particles with an average particle size of 0.5-0.8 μm, 30-40 Vol% of submicron particles with an average particle size of 0.3-0.5 μm, and 10-20 Vol% of submicron particles with an average particle size of 0.1-0.3 μm.
5. The mold release agent for crystallization of ultra-thin glass according to claim 4, characterized in that the sub-micron beta silicon carbide has point defects of 0.3% or less by itself.
6. The mold release agent for ultra-thin glass crystallization process according to claim 1, characterized in that the wetting dispersant is one or more of salt solution of unsaturated polyamine amide and/or acidic polyester, the defoaming agent is polydimethylsiloxane, the surface auxiliary agent is polysiloxane and/or polyacrylate, SiO in the silica sol is SiO in the silica sol2The content of (B) is 30 wt%.
7. The mold release agent for crystallization of ultra-thin glass according to claim 2, characterized in that the PH modifier is one or more of citric acid, sorbic acid, sodium bicarbonate or disodium hydrogen phosphate.
8. A method for preparing the mold release agent for ultra-thin glass crystallization process of claim 1, comprising the steps of:
the method comprises the following steps: uniformly mixing 4-20 wt%, 8-40 wt%, 20-80 wt% of submicron hexagonal boron nitride, submicron beta silicon carbide and silica sol in softened water, and gradually adding 1-2 wt% of wetting dispersant in the stirring process until the solution is uniform and off-white;
step two: carrying out ultrasonic oscillation deflocculation on the solution obtained in the first step for 4-5 hours in a water bath, setting the ultrasonic power of an ultrasonic cleaning machine to be 400-500W, and setting the temperature of the ultrasonic cleaning machine to be 50-80 ℃;
step three: slowly stirring the uniform solution obtained in the second step for 2-3 hours after 0.01-0.05 wt% of defoaming agent is added, adding 0-2 wt% of PH regulator in the stirring process, and regulating the PH of the solution to be neutral;
step four: and (3) adding 0.4-1.2 wt% of surface auxiliary agent into the solution obtained in the step three, continuously stirring at a low speed for 0.5-1 h, and fully reacting to obtain the release agent for the crystallization process of the ultrathin glass.
9. The method for preparing a mold release agent for ultra-thin glass crystallization process according to claim 8, wherein the wetting dispersant in the first step is one or more of salt solution of unsaturated polyamine amide and/or acid polyester, SiO in silica sol2The content of (B) is 30 wt%; the defoaming agent in the third step is polydimethylsiloxane; and the surface auxiliary agent in the fourth step is polysiloxane and/or polyacrylate.
10. The method for using the mold release agent for the crystallization process of ultra-thin glass as claimed in claim 1, wherein the mold release agent is first sprayed on the surface of the ultra-thin glass substrate by spraying for 2 times, each time is performed in different directions to ensure that no spray leakage occurs, the interval between each spraying is 1 minute, the next spraying is performed after the previous spraying is dried and cured, then the ultra-thin glass substrates are stacked in sequence in an oven at 120 ℃, and finally the ultra-thin glass substrates are dried at 80-105 ℃.
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Inventor after: Zhang Fujun Inventor after: Zhu Kaidi Inventor after: Hao Zhenbang Inventor after: Cui Kaimin Inventor after: Zhang Jihong Inventor before: Zhang Fujun Inventor before: Liu Jingzhong Inventor before: Zhu Kaidi Inventor before: Hao Zhenbang Inventor before: Cui Kaimin Inventor before: Zhang Jihong |