An integrated blow molding process for a relief wine glass

Abstract

The application relates to the field of glass container manufacturing and discloses an integrated blow molding process for a relief wine cup, which comprises the following components in mass parts: pentaerythritol tetranonanoate 58-66 parts; polyisobutylene 18-20 parts; polyisobutylene succinimide dispersant 1-2 parts; zinc-boron-silicon low-melting-point glass powder 10-15 parts; hexagonal boron nitride 3-5 parts; wherein: the pentaerythritol tetranonanoate and the polyisobutylene serve as a continuous-phase organic carrier for controlled pure volatilization when contacting a high-temperature mold surface and for forming a solid powder deposition layer without gas-phase explosive boiling on the mold surface; the zinc-boron-silicon low-melting-point glass powder is used for triggering solid-liquid phase change absorption of latent heat of fusion when contacting a high-temperature glass melt to realize transient quenching of a glass surface. By adopting the pentaerythritol tetranonanoate and the polyisobutylene as anhydrous continuous phases, controlled pure volatilization can be realized after contacting a high-temperature mold, and gas-phase disturbance caused by boiling of a traditional water-based release agent when heated is avoided.

Description

Technical Field

[0001] This invention relates to the field of glass container manufacturing, specifically to a one-piece blow molding process for embossed wine glasses. Background Technology

[0002] In the automated production of relief-carved glass wine glasses, the performance of the release agent directly affects the surface quality and dimensional accuracy of the product. Existing release technologies mostly use water-based emulsions or conventional mineral oils as carriers, mixed with solid lubricants such as graphite.

[0003] When water-based mold release agents come into contact with the high-temperature mold surface (450°C–500°C), the water undergoes a sudden and violent boiling. This rapid expansion of the gas phase volume generates microscopic airflow disturbances, impacting the softened, high-temperature glass surface and leaving pits or pores on the glass surface, compromising the product's transparency and optical smoothness. When conventional mineral oil is used as a carrier, the organic components are prone to pyrolysis and incomplete combustion at high temperatures, forming coked carbon deposits that accumulate in the mold grooves. These carbon deposits not only contaminate the glass surface, causing black spots, but also alter the original contours of the mold relief with increased production cycles, reducing the cleanliness of the product.

[0004] Existing mold release agents primarily function as interfacial lubricants, and their heat transfer relies on the passive heat dissipation of the mold metal. After the glass droplets fill the relief grooves, the interfacial cooling rate is insufficient, and the viscosity of the glass surface cannot quickly rise to the required strength before mold opening. This results in the glass material at the relief edges easily softening and shrinking due to gravity or mold traction at the moment of mold separation, causing blurred relief patterns or dimensional deviations. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an integral blow molding process for embossed wine glasses, which solves the problem that the glass material at the edge of the embossed design is prone to secondary softening and shrinkage due to gravity or mold traction.

[0006] To achieve the above objectives, the present invention provides the following technical solution: an anhydrous demolding composition for integral blow molding of relief wine glasses, comprising the following parts by weight:

[0007] Pentaerythritol tetranonanoate: 58–66 parts;

[0008] Polyisobutylene: 18-20 parts;

[0009] Polyisobutylene succinimide dispersant: 1-2 parts;

[0010] Zinc borosilicate low-melting-point glass powder: 10-15 parts;

[0011] Hexagonal boron nitride: 3-5 parts.

[0012] Preferably, the pentaerythritol tetranonanoate and polyisobutylene serve as a continuous organic carrier, used to undergo controlled pure volatilization upon contact with the high-temperature mold surface and form a solid powder deposition layer on the mold surface without gas phase boiling; the zinc borosilicate low-melting-point glass powder is used to trigger a solid-liquid phase transition upon contact with the high-temperature glass melt to absorb the latent heat of fusion and achieve transient quenching of the glass surface, and together with the hexagonal boron nitride, constructs a heterogeneous composite lubricating film of high viscosity fluid and layered solid; the particle size distribution D50 of the zinc borosilicate low-melting-point glass powder is between 3.0 μm and 8.0 μm, based on the molar percentage of each component in the final glass product; the zinc borosilicate low-melting-point glass powder is made by melting and quenching the following components in water and then pulverizing: 37%–45% zinc oxide, 40%–50% boron oxide, 5%–13% silicon dioxide, 1%–4% sodium oxide, and 1%–4% potassium oxide.

[0013] A method for preparing polyisobutylene succinimide dispersant includes the following steps:

[0014] a. Highly reactive polyisobutylene with a number average molecular weight of 1000 and a terminal vinylidene double bond mass fraction greater than or equal to 80.0% is added to a reaction vessel with maleic anhydride at a molar ratio of 1:1.1 to 1:1.2. The mixture is heated to 200℃ to 220℃ under nitrogen protection and reacted at a constant temperature for 4 to 6 hours. Unreacted maleic anhydride is removed by depressurization to obtain the intermediate polyisobutylene succinic anhydride.

[0015] b. Cool the polyisobutylene succinic anhydride obtained in the first step to 100°C, and add tetraethylenepentamine dropwise at a molar ratio of polyisobutylene succinic anhydride to tetraethylenepentamine of 1:0.4 to 1:0.5. After the addition is complete, raise the temperature to 150°C to 160°C, reflux for 3 to 4 hours, and remove the water generated in the reaction using a water separator to obtain polyisobutylene succinimide dispersant.

[0016] Preferably, the polyisobutylene is a homopolymer of isobutylene with a number average molecular weight between 1000 and 2500 and a molecular weight distribution index between 1.5 and 2.0; the hexagonal boron nitride has a lamellar cleavage structure, a median particle size D50 between 1.0 and 3.0 μm, and a purity greater than or equal to 99.0%.

[0017] Preferred, the one-piece blow molding process for the embossed wine glass using an anhydrous release composition includes the following steps:

[0018] S1. The components in the anhydrous release composition are sheared, mixed and ground according to the set weight percentage to obtain a homogenized anhydrous dynamic release suspension.

[0019] S2. Before the glass material drips into the molding mold base, the anhydrous dynamic demolding suspension prepared in step S1 is atomized and sprayed onto the inner wall of the mold and the relief groove, which are maintained at a set low temperature, to form a coating.

[0020] S3. Drop silicate glass material into the molding mold base, introduce compressed air for positive pressure blowing, so that the glass material droplet extends and fills the relief groove.

[0021] S4. After the blow molding and holding time is set, the mold is opened, the formed glass is taken out and sent to the annealing furnace to perform the stress relief curve and cool, and the relief wine glass is obtained.

[0022] Preferably, the specific implementation of S1 is as follows: In a jacketed high-shear dispersion vessel, pentaerythritol tetranonanoate and polyisobutylene are added, and the system is heated to 60℃~80℃. Polyisobutylene succinimide dispersant is added, and the mixture is kept at a constant temperature and mixed for 30~45 minutes at a stirring speed of 500~800 rpm. The stirring speed is increased to 2000~3000 rpm, and zinc borosilicate low-melting-point glass powder and hexagonal boron nitride are added. The mixture is dispersed under high shear conditions for 1.0~2.0 hours. The coarse suspension is pumped into a colloid mill for 2~3 cycles of grinding, and after filtration through a 300-mesh filter, an anhydrous dynamic release suspension is obtained.

[0023] Preferably, in step S2: the working temperature of the molding die substrate is maintained at 450°C to 500°C; 1.5 to 2.0 seconds before the glass material drips in, a pneumatic atomizing spray gun is used to spray the coating at a working air pressure of 0.3 MPa to 0.5 MPa; and the wet film thickness of the coating is controlled to be 15 micrometers to 25 micrometers.

[0024] Preferably, in step S3: the initial temperature of the silicate glass droplet falling into the molding die substrate is controlled at 1000℃~1100℃; the positive pressure parameter of the introduced compressed air is controlled between 0.2 MPa and 0.4 MPa.

[0025] Preferably, in step S4: the blowing and holding time is controlled between 2 and 4 seconds; after being sent into the annealing furnace, stress relief is performed within the temperature range of 550°C to room temperature.

[0026] This invention provides a one-piece blow molding process for embossed wine glasses. It offers the following advantages:

[0027] 1. This invention utilizes pentaerythritol tetranonanoate and polyisobutylene as an anhydrous continuous phase, which allows for controlled and pure volatilization upon contact with a high-temperature mold. This avoids the gas phase disturbances caused by the boiling of traditional water-based mold release agents upon heating, and also avoids the problem of high-temperature coking and carbonization of conventional mineral oils. This enables the elimination of pores and black spots on the surface of glass products, thereby improving the surface smoothness of the products.

[0028] 2. The composition of this invention contains a specific ratio of zinc borosilicate low-melting-point glass powder. When it comes into contact with high-temperature molten glass, it can rapidly undergo a solid-liquid phase transition and absorb the latent heat of fusion. The heat absorption process achieves transient cooling of the glass molten surface, causing its local viscosity to increase and quickly solidify within the relief groove of the mold, suppressing secondary softening and dimensional shrinkage after mold opening, and improving the dimensional accuracy of the relief structure.

[0029] 3. This invention utilizes molten zinc borosilicate glass as a fluid dynamics carrier, combined with hexagonal boron nitride with interlayer cleavage structure, to form a heterogeneous composite lubricating film combining a high-viscosity fluid and layered solid at the interface between the mold and the glass product. This composite lubricating film provides lower shear yield stress, reducing frictional resistance during mold opening of complex relief structures and achieving non-destructive demolding of the product. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the preparation process steps of the present invention. Detailed Implementation

[0031] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] This invention provides an anhydrous demolding composition for integral blow molding of embossed wine glasses, comprising the following parts by weight:

[0033] Pentaerythritol tetranonanoate: 58-66 parts; polyisobutylene: 18-20 parts; pentaerythritol tetranonanoate and polyisobutylene serve as a continuous phase organic carrier, used to achieve controlled pure volatilization upon contact with the high-temperature mold surface and form a solid powder deposition layer on the mold surface without gas phase boiling; polyisobutylene succinimide dispersant: 1-2 parts, with a number average molecular weight between 1000 and 2500 and a molecular weight distribution index between 1.5 and 2.0; a. Highly reactive polyisobutylene with a number average molecular weight of 1000 and a terminal vinylidene double bond mass fraction greater than or equal to 80.0% is reacted with maleic anhydride. Add the polyisobutylene succinic anhydride to the reactor at a molar ratio of 1:1.1 to 1:1.2, and heat it to 200℃ to 220℃ under nitrogen protection for 4 to 6 hours. Remove unreacted maleic anhydride under reduced pressure to obtain the intermediate polyisobutylene succinic anhydride; b) Cool the polyisobutylene succinic anhydride obtained in the first step to 100℃, and add tetraethylenepentamine dropwise at a molar ratio of 1:0.4 to 1:0.5. After the addition is complete, heat it to 150℃ to 160℃, reflux it for 3 to 4 hours, and remove the water generated in the reaction using a water separator to obtain the polyisobutylene succinimide dispersant. Zinc borosilicate low-melting-point glass powder: 10-15 parts. This powder is used to trigger a solid-liquid phase transition upon contact with high-temperature molten glass, absorbing latent heat of fusion to achieve transient cooling of the glass surface. It also works with hexagonal boron nitride to construct a heterogeneous composite lubricating film of high-viscosity fluid and layered solid. The particle size distribution (D50) of the zinc borosilicate low-melting-point glass powder is between 3.0 μm and 8.0 μm, based on the molar percentage of each component in the final glass product. The borosilicate low-melting-point glass powder is prepared by melting, quenching, and pulverizing the following components: 37%-45% zinc oxide, 40%-50% boron oxide, 5%-13% silicon dioxide, 1%-4% sodium oxide, and 1%-4% potassium oxide. Hexagonal boron nitride: 3-5 parts. Hexagonal boron nitride has a layered cleavage structure, a median particle size (D50) between 1.0 and 3.0 μm, and a purity greater than or equal to 99.0%.

[0034] Please see the appendix Figure 1 The process of blow molding an embossed wine glass using an anhydrous release composition includes the following steps:

[0035] S1. The components in the anhydrous release composition are sheared, mixed, and ground according to a set weight percentage to obtain a homogenized anhydrous dynamic release suspension. Specifically, in a jacketed high-shear dispersion vessel, pentaerythritol tetranonanoate and polyisobutylene are added, and the system is heated to 60℃~80℃. Polyisobutylene succinimide dispersant is added, and the mixture is kept at a constant temperature and mixed for 30~45 minutes at a stirring speed of 500~800 rpm. The stirring speed is increased to 2000~3000 rpm, and zinc borosilicate low-melting-point glass powder and hexagonal boron nitride are added. The mixture is dispersed under high shear conditions for 1.0~2.0 hours. The coarse suspension is pumped into a colloid mill for 2~3 cycles of grinding, and then filtered through a 300-mesh filter to obtain the anhydrous dynamic release suspension.

[0036] S2. Before the glass material drips into the molding die substrate, the anhydrous dynamic release suspension prepared in step S1 is atomized and sprayed onto the inner wall of the mold and the relief groove, which are maintained at a set bottom temperature, to form a coating: the working bottom temperature of the molding die substrate is controlled to be maintained at 450℃~500℃; 1.5 seconds to 2.0 seconds before the glass material drips in, a pneumatic atomizing spray gun is used to spray at a working air pressure of 0.3 MPa~0.5 MPa; the wet film thickness of the coating is controlled to be 15 micrometers~25 micrometers.

[0037] S3. Drop silicate glass material into the molding die substrate and introduce compressed air for positive pressure blowing, so that the glass material droplet extends and fills the relief groove; the preparation conditions of the nano-delivery system are: the initial temperature of the silicate glass material droplet falling into the molding die substrate is controlled at 1000℃~1100℃; the positive pressure parameter of the introduced compressed air is controlled between 0.2 MPa and 0.4 MPa.

[0038] S4. After the blown pressure setting time, the mold is opened, the formed glass is taken out and sent to the annealing furnace to perform stress relief curve and cool, to obtain the relief wine glass: the blown pressure setting time is controlled between 2 and 4 seconds; after being sent to the annealing furnace, stress relief is performed within the temperature range of 550℃ to room temperature.

[0039] To facilitate understanding of this technical solution, the following embodiments are proposed based on the same inventive concept:

[0040] Example 1:

[0041] The specific formula includes the following parts by weight: pentaerythritol tetranonanoate: 64 parts; polyisobutylene: 18 parts; polyisobutylene succinimide dispersant: 1.5 parts; zinc borosilicate low-melting-point glass powder: 12.5 parts; hexagonal boron nitride: 4 parts;

[0042] S1. In a jacketed high-shear dispersion vessel, add 64 parts by weight of pentaerythritol tetranonanoate and 18 parts by weight of polyisobutylene. Turn on the heat transfer oil to heat the system to 70°C. Add 1.5% of the polyisobutylene succinimide dispersant prepared in Preparation Example 2 and mix at a constant temperature for 40 minutes with a stirring speed of 600 rpm. Increase the stirring speed to 2500 rpm and add 12.5% ​​of the zinc borosilicate low-melting-point glass powder prepared in Preparation Example 5 and 4.0% of hexagonal boron nitride. Maintain high-shear dispersion for 1.5 hours. Pump the coarse suspension into a colloid mill for two cycles of grinding. After filtering through a 300-mesh filter, obtain an anhydrous dynamic release suspension.

[0043] S2. In the forming machine, the forming mold substrate is maintained at a working temperature of 475°C. 1.8 seconds before the glass material at 1050°C drips, the anhydrous dynamic release suspension prepared in step one is sprayed onto the inner wall of the mold and the relief groove using a pneumatic atomizing spray gun with a working air pressure of 0.4 MPa, forming a coating with a wet film thickness of 20 micrometers.

[0044] S3. Drop silicate glass material at a temperature of 1050℃ into the mold, introduce 0.3 MPa compressed air for positive pressure blowing, so that the droplet extends and fills the relief groove.

[0045] S4. After blowing and holding pressure for 3 seconds, open the mold, take out the formed glass and send it into the annealing furnace. Perform stress relief curve within the range of 550℃ to room temperature and cool to obtain the relief wine glass.

[0046] Example 2:

[0047] The specific formula includes the following parts by weight: pentaerythritol tetranonanoate: 58 parts; polyisobutylene: 20 parts; polyisobutylene succinimide dispersant: 2 parts; zinc borosilicate low melting point glass powder: 15 parts; hexagonal boron nitride: 5 parts;

[0048] S1. In a jacketed high-shear dispersion vessel, add 58 parts by mass of pentaerythritol tetranonanoate and 20 parts by mass of polyisobutylene. Turn on the heat transfer oil to heat the system to 80°C. Add 2 parts by mass of polyisobutylene succinimide dispersant prepared in Preparation Example 3. Mix at a constant temperature for 45 minutes at a stirring speed of 800 rpm. Increase the stirring speed to 3000 rpm. Add 15 parts by mass of zinc borosilicate low-melting-point glass powder prepared in Preparation Example 6 and 5 parts by mass of hexagonal boron nitride. Maintain high-shear dispersion for 2.0 hours. Pump the coarse suspension into a colloid mill for three cycles of grinding. After filtering through a 300-mesh filter, obtain an anhydrous dynamic release suspension.

[0049] S2. In the forming machine, the forming mold substrate is maintained at a working temperature of 475°C. 1.8 seconds before the glass material at 1050°C drips, the anhydrous dynamic release suspension prepared in step one is sprayed onto the inner wall of the mold and the relief groove using a pneumatic atomizing spray gun with a working air pressure of 0.4 MPa, forming a coating with a wet film thickness of 20 micrometers.

[0050] S3. Drop silicate glass material at a temperature of 1050℃ into the mold, introduce 0.3 MPa compressed air for positive pressure blowing, so that the droplet extends and fills the relief groove.

[0051] S4. After blowing and holding pressure for 3 seconds, open the mold, take out the formed glass and send it into the annealing furnace. Perform stress relief curve within the range of 550℃ to room temperature and cool to obtain the relief wine glass.

[0052] Example 3:

[0053] The specific formula includes the following parts by weight: pentaerythritol tetranonanoate: 66 parts; polyisobutylene: 20 parts; polyisobutylene succinimide dispersant: 1 part; zinc borosilicate low melting point glass powder: 10 parts; hexagonal boron nitride: 3 parts;

[0054] S1. In a jacketed high-shear dispersion vessel, add 66 parts by mass of pentaerythritol tetranonanoate and 20 parts by mass of polyisobutylene. Turn on the heat transfer oil to heat the system to 60°C. Add 1 part of polyisobutylene succinimide dispersant prepared in Preparation Example 1. Mix at a constant temperature for 30 minutes at a stirring speed of 500 rpm. Increase the stirring speed to 2000 rpm. Add 10 parts of zinc borosilicate low-melting-point glass powder prepared in Preparation Example 4 and 3 parts of hexagonal boron nitride. Maintain high-shear dispersion for 1.0 hour. Pump the coarse suspension into a colloid mill for two cycles of grinding. After filtering through a 300-mesh filter, obtain an anhydrous dynamic release suspension.

[0055] S2. In the forming machine, the forming mold substrate is maintained at a working temperature of 475°C. 1.8 seconds before the glass material at 1050°C drips, the anhydrous dynamic release suspension prepared in step one is sprayed onto the inner wall of the mold and the relief groove using a pneumatic atomizing spray gun with a working air pressure of 0.4 MPa, forming a coating with a wet film thickness of 20 micrometers.

[0056] S3. Drop silicate glass material at a temperature of 1050℃ into the mold, introduce 0.3 MPa compressed air for positive pressure blowing, so that the droplet extends and fills the relief groove.

[0057] S4. After blowing and holding pressure for 3 seconds, open the mold, take out the formed glass and send it into the annealing furnace. Perform stress relief curve within the range of 550℃ to room temperature and cool to obtain the relief wine glass.

[0058] Example 4:

[0059] The specific formula includes the following parts by weight: pentaerythritol tetranonanoate: 64 parts; polyisobutylene: 18 parts; polyisobutylene succinimide dispersant: 1.5 parts; zinc borosilicate low-melting-point glass powder: 12.5 parts; hexagonal boron nitride: 4 parts;

[0060] S1. In a jacketed high-shear dispersion vessel, add 64 parts by mass of pentaerythritol tetranonanoate and 18 parts by mass of polyisobutylene. Turn on the heat transfer oil to heat the system to 70°C. Add 1.5 parts by mass of polyisobutylene succinimide dispersant prepared in Preparation Example 2. Mix at a constant temperature for 40 minutes at a stirring speed of 600 rpm. Increase the stirring speed to 2500 rpm. Add 12.5% ​​of zinc borosilicate low-melting-point glass powder prepared in Preparation Example 6 and 4 parts by mass of hexagonal boron nitride. Maintain high-shear dispersion for 1.5 hours. Pump the coarse suspension into a colloid mill for two cycles of grinding. After filtering through a 300-mesh filter, obtain an anhydrous dynamic release suspension.

[0061] S2. In the forming machine, the forming mold substrate is maintained at a working temperature of 500°C. 1.5 seconds before the glass material at 1100°C drips, the anhydrous dynamic release suspension prepared in step one is sprayed onto the inner wall of the mold and the relief groove using a pneumatic atomizing spray gun with a working air pressure of 0.5 MPa to form a coating with a wet film thickness of 15 micrometers.

[0062] S3. Drop silicate glass material at 1100℃ into the mold, introduce 0.4 MPa compressed air for positive pressure blowing, so that the droplet extends and fills the relief groove.

[0063] S4. After blowing and holding pressure for 2 seconds, open the mold, take out the formed glass and send it into the annealing furnace. Perform stress relief curve within the range of 550℃ to room temperature and cool to obtain the relief wine glass.

[0064] Example 5:

[0065] The specific formula includes the following parts by weight: pentaerythritol tetranonanoate: 64 parts; polyisobutylene: 18 parts; polyisobutylene succinimide dispersant: 1.5 parts; zinc borosilicate low-melting-point glass powder: 12.5 parts; hexagonal boron nitride: 4 parts;

[0066] S1. In a jacketed high-shear dispersion vessel, add 64 parts by mass of pentaerythritol tetranonanoate and 18 parts by mass of polyisobutylene. Turn on the heat transfer oil to heat the system to 70°C. Add 1.5 parts by mass of polyisobutylene succinimide dispersant prepared in Preparation Example 2. Mix at a constant temperature for 40 minutes at a stirring speed of 600 rpm. Increase the stirring speed to 2500 rpm. Add 12.5 parts by mass of zinc borosilicate low-melting-point glass powder prepared in Preparation Example 4 and 4 parts by mass of hexagonal boron nitride. Maintain high-shear dispersion for 1.5 hours. Pump the coarse suspension into a colloid mill for two cycles of grinding. After filtering through a 300-mesh filter, obtain an anhydrous dynamic release suspension.

[0067] S2. In the forming machine, the forming mold substrate is maintained at a working temperature of 450°C. 2.0 seconds before the glass material at 1000°C drips, the anhydrous dynamic release suspension prepared in step one is sprayed onto the inner wall of the mold and the relief groove using a pneumatic atomizing spray gun with a working air pressure of 0.3 MPa to form a coating with a wet film thickness of 25 micrometers.

[0068] S3. Drop silicate glass material at a temperature of 1000℃ into the mold, introduce 0.2 MPa compressed air for positive pressure blowing, so that the droplet extends and fills the relief groove.

[0069] S4. After blowing and holding pressure for 4 seconds, open the mold, take out the formed glass and send it into the annealing furnace. Perform stress relief curve within the range of 550℃ to room temperature and cool to obtain the relief wine glass.

[0070] Comparative Example 1: Compared with Example 1, a commercially available conventional mineral oil and graphite powder mixture was used instead of the anhydrous dynamic release suspension of the present invention, and all other aspects were the same.

[0071] Traditional processes rely on the mold metal, which has extremely low thermal conductivity, for passive heat transfer, making it impossible to achieve instantaneous cooling of the interface. Furthermore, the demolding interface cannot achieve homogeneous fusion without residue, which not only leads to secondary softening and shrinkage of the relief edges, but also causes traditional mineral oil to coke and carbonize at high temperatures, making it impossible to guarantee extremely high optical smoothness and purity of the product surface.

[0072] Comparative Example 2: Compared with Example 1, in the preparation of the anhydrous dynamic release suspension, the zinc borosilicate low melting point glass powder obtained from Preparation Example 5 was completely removed and replaced with an equal mass of pentaerythritol tetranonanoate to make up the balance, and all other aspects were the same.

[0073] This comparative example lacks strict thermodynamic threshold control and a phase change endothermic mechanism. When the high-temperature glass melt is pressed under high pressure onto the coating, a phase change from solid to liquid cannot occur, and the enormous latent heat of fusion cannot be absorbed. Therefore, it is impossible to rapidly reduce the temperature of the glass surface layer in close contact with the mold, causing its viscosity to jump exponentially to 10. 7Above dPa·s, the molten glass cannot be instantly frozen within the deep cavity relief. Simultaneously, due to the lack of molten glass as a hydrodynamic carrier, it cannot form a heterogeneous composite lubricating film of high-viscosity fluid and layered solid with the pre-placed lamellar hexagonal boron nitride.

[0074] Comparative Example 3: Compared with Example 1, in the preparation of the anhydrous dynamic release suspension, hexagonal boron nitride was completely removed and replaced with an equal mass of pentaerythritol tetranonanoate to make up the balance, and all other aspects were the same.

[0075] This comparative example lacks the key solid lubrication synergy in the assembly mechanism of the composite lubrication layer. Under droplet impact, although low-melting-point glass powder can undergo phase change and absorb heat to provide a molten glass film as a hydrodynamic carrier, the lack of extremely low extreme pressure shear yield stress provided by the interlayer cleavage of hexagonal boron nitride makes it impossible to form a heterogeneous composite lubrication film of high viscosity fluid and layered solid at the interface between the mold and the glass product. The friction coefficient increases significantly, making it impossible to ensure the non-destructive peeling of complex relief structures during mold opening.

[0076] Comparative Example 4: Compared with Example 1, in the preparation of the anhydrous dynamic release suspension, conventional high-melting-point glass powder with a melting point greater than 800°C was used to replace the zinc borosilicate low-melting-point glass powder prepared in Preparation Example 5, and all other aspects were the same.

[0077] This comparative example violates strict thermodynamic threshold control. Due to the excessively high melting point of the glass powder, the high-temperature glass droplets cannot instantly break through the melting threshold to undergo a drastic solid-liquid phase transition within an extremely short contact time. The coating cannot absorb the enormous latent heat of fusion, causing the instantaneous quenching effect to fail, and the rheological viscosity of the glass surface cannot jump above the softening point. At the same time, because it fails to melt into a liquid glass film with a relatively low viscosity of 10¹ to 10² dPa·s, the high-temperature hydrodynamic lubrication mechanism also fails.

[0078] Comparative Example 5: Compared with Example 1, an oil-in-water dynamic release emulsion containing 15% deionized water and 10% zinc oxalate solid particles was used instead of the anhydrous dynamic release suspension of the present invention, and all other aspects were the same.

[0079] This comparative example completely disrupts the latency stability and zero-gas-phase defect suppression mechanism. Due to the presence of water and easily decomposable gas-producing salts in the system, the coating cannot maintain thermodynamic stability in the solid state during the 1.8 seconds of waiting for material droplets, resulting in severe premature boiling dissipation. Upon high-temperature triggering, a rapidly expanding gas phase, such as water vapor and carbon dioxide, is generated. The micro-airflow disturbances violently impact the soft, high-temperature glass surface, fundamentally causing pores and micro-pit defects on the product surface, making it impossible to exhibit extremely high optical smoothness.

[0080] Experimental Example: Macroscopic rheology and storage stability testing of the suspension in this case study:

[0081] Experimental procedure: According to the composition formulations of Examples 1 to 5 and Comparative Examples 1 to 5, 100 mL of each prepared and fully homogenized suspension or emulsion sample was measured and injected into a dry 100 mL stoppered glass graduated cylinder to avoid generating air bubbles.

[0082] Seal the graduated cylinders with glass stoppers and place them in a constant temperature, light-proof shaking incubator set at 25°C to maintain absolute stillness.

[0083] The volume of the transparent clear liquid layer precipitated at the top of the graduated cylinder was read at time points of 1 day, 3 days, 7 days and 14 days respectively.

[0084] Record the data and calculate the settlement rate at each time point. The calculation formula is: Settlement rate (%) = (Volume of clear liquid layer / 100) × 100%. Take the arithmetic mean of multiple parallel tests.

[0085] Table 1. Settling rate test data of the compositions of each embodiment and comparative example under static temperature.

[0086] Group 1-day settlement rate (%) 3-day settlement rate (%) 7-day settlement rate (%) 14-day settlement rate (%) Example 1 0.0 0.2 0.8 1.4 Example 2 0.0 0.1 0.6 1.1 Example 3 0.1 0.4 1.2 2.3 Example 4 0.0 0.3 0.7 1.6 Example 5 0.0 0.2 0.9 1.5 Comparative Example 1 0.5 2.1 5.4 11.2 Comparative Example 2 0.0 0.1 0.3 0.8 Comparative Example 3 0.1 0.3 1.1 1.9 Comparative Example 4 0.2 0.6 1.5 2.8 Comparative Example 5 1.2 4.5 12.7 24.3

[0087] According to the data in Table 1, the anhydrous dynamic release suspensions of Examples 1 to 5 maintained a sedimentation rate of less than 2.5% during the 14-day long-term static test, demonstrating high standard rheological stability.

[0088] This verifies the effectiveness of the mechanism of introducing a customized polyisobutylene succinimide polymeric dispersant into the base oil phase in this formulation. The polar polyamine groups in the polyisobutylene succinimide molecule can anchor to the inorganic surfaces of zinc borosilicate glass powder and hexagonal boron nitride particles. Its nonpolar polyisobutylene long chains are extended in the pentaerythritol tetranonanoate continuous phase, constructing a steric hindrance layer and overcoming the van der Waals aggregation tendency of high-density inorganic powders. The film-forming agent polyisobutylene in the formulation increases the macroscopic kinematic viscosity of the base oil. According to Stokes's law of sedimentation, the increase in continuous phase viscosity reduces the terminal settling velocity of solid particles.

[0089] In contrast, Comparative Example 5, which used a water-in-oil emulsion system, showed a sudden increase in sedimentation rate to 12.7% after 7 days of standing, reaching 24.3% after 14 days, with macroscopic phase separation occurring. This demonstrates that multiphase emulsion systems exhibit thermodynamic instability under a gravitational field, making them prone to droplet aggregation and demulsification / water separation.

[0090] The conventional mineral oil-graphite system in Comparative Example 1 lacks targeted polymeric dispersants and viscosity adjustment mechanisms, and its sedimentation rate reaches 11.2% after 14 days. Under these conditions, the component distribution exhibits a severe gradient difference.

[0091] Comparative Example 2 has a lower absolute sedimentation rate of 0.8% due to the removal of zinc borosilicate glass powder with higher density. This phenomenon is an inevitable result of reducing the physical load on the solid in the system. However, this formulation loses the physical basis for phase change endothermic reaction in the subsequent molding process.

[0092] Test results show that the technical solution of this invention achieves long-term physical storage stability of high solids content phase change inorganic powder system by combining anhydrous continuous phase with steric dispersant, ensuring the uniformity of material composition during subsequent continuous automatic spraying operation of row and column machines, and avoiding engineering problems such as nozzle clogging and uneven coating thickness on mold surface caused by particle sedimentation.

[0093] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A waterless release composition for integral blow molding of relief wine glasses, characterized in that, Includes the following mass fractions: Pentaerythritol tetranonanoate: 58–66 parts; Polyisobutylene: 18-20 parts; Polyisobutylene succinimide dispersant: 1-2 parts; Zinc borosilicate low-melting-point glass powder: 10-15 parts; Hexagonal boron nitride: 3-5 parts.

2. The anhydrous demolding composition for integral blow molding of embossed wine glasses according to claim 1, characterized in that, in: The pentaerythritol tetranonanoate and polyisobutylene serve as continuous phase organic carriers, enabling controlled pure volatilization upon contact with the high-temperature mold surface and forming a solid powder deposition layer on the mold surface without gas phase boiling. The zinc borosilicate low-melting-point glass powder triggers a solid-liquid phase transition upon contact with the high-temperature glass melt, absorbing the latent heat of fusion to achieve transient quenching of the glass surface, and together with the hexagonal boron nitride, constructs a heterogeneous composite lubricating film of high-viscosity fluid and layered solid. The particle size distribution D50 of the zinc borosilicate low-melting-point glass powder is between 3.0 μm and 8.0 μm, based on the molar percentage of each component in the final glass product. The zinc borosilicate low-melting-point glass powder is made by melting, quenching, and pulverizing the following components: 37%–45% zinc oxide, 40%–50% boron oxide, 5%–13% silicon dioxide, 1%–4% sodium oxide, and 1%–4% potassium oxide.

3. The anhydrous demolding composition for integral blow molding of relief wine glasses according to claim 1, characterized in that, The preparation method of the polyisobutylene succinimide dispersant includes the following steps: a. Highly reactive polyisobutylene with a number average molecular weight of 1000 and a terminal vinylidene double bond mass fraction greater than or equal to 80.0% is added to a reaction vessel with maleic anhydride at a molar ratio of 1:1.1 to 1:1.

2. The mixture is heated to 200℃ to 220℃ under nitrogen protection and reacted at a constant temperature for 4 to 6 hours. Unreacted maleic anhydride is removed by depressurization to obtain the intermediate polyisobutylene succinic anhydride. b. Cool the polyisobutylene succinic anhydride obtained in the first step to 100°C, and add tetraethylenepentamine dropwise at a molar ratio of polyisobutylene succinic anhydride to tetraethylenepentamine of 1:0.4 to 1:0.

5. After the addition is complete, raise the temperature to 150°C to 160°C, reflux for 3 to 4 hours, and remove the water generated in the reaction using a water separator to obtain polyisobutylene succinimide dispersant.

4. The anhydrous demolding composition for integral blow molding of relief wine glasses according to claim 1, characterized in that: The polyisobutylene is a homopolymer of isobutylene with a number-average molecular weight between 1000 and 2500 and a molecular weight distribution index between 1.5 and 2.

0. The hexagonal boron nitride has a lamellar cleavage structure with a median particle size D50 between 1.0 and 3.0 μm and a purity greater than or equal to 99.0%.

5. A process for integral blow molding of relief wine glasses using the anhydrous release composition according to any one of claims 1 to 4, characterized in that, Includes the following steps: S1. The components in the anhydrous release composition are sheared, mixed and ground according to the set weight percentage to obtain a homogenized anhydrous dynamic release suspension. S2. Before the glass material drips into the molding mold base, the anhydrous dynamic demolding suspension prepared in step S1 is atomized and sprayed onto the inner wall of the mold and the relief groove, which are maintained at a set low temperature, to form a coating. S3. Drop silicate glass material into the molding mold base, introduce compressed air for positive pressure blowing, so that the glass material droplet extends and fills the relief groove. S4. After the blow molding and holding time is set, the mold is opened, the formed glass is taken out and sent to the annealing furnace to perform the stress relief curve and cool, and the relief wine glass is obtained.

6. The molding process according to claim 5, characterized in that, The specific implementation of S1 is as follows: In a jacketed high-shear dispersion vessel, pentaerythritol tetranonanoate and polyisobutylene are added, and the system is heated to 60℃~80℃. Polyisobutylene succinimide dispersant is added, and the mixture is kept at a constant temperature and mixed for 30~45 minutes at a stirring speed of 500~800 rpm. The stirring speed is increased to 2000~3000 rpm, and zinc borosilicate low-melting-point glass powder and hexagonal boron nitride are added. The mixture is dispersed under high shear conditions for 1.0~2.0 hours. The coarse suspension is pumped into a colloid mill for 2~3 cycles of grinding, and after filtration through a 300-mesh filter, an anhydrous dynamic release suspension is obtained.

7. The molding process according to claim 5, characterized in that, In step S2: the working temperature of the molding die substrate is maintained at 450℃~500℃; 1.5 seconds to 2.0 seconds before the glass material drips in, a pneumatic atomizing spray gun is used to spray the coating at a working air pressure of 0.3 MPa~0.5 MPa; the wet film thickness of the coating is controlled to be 15 micrometers~25 micrometers.

8. The molding process according to claim 5, characterized in that, In S3: the initial temperature of the silicate glass droplets falling into the molding die substrate is controlled at 1000℃~1100℃; the positive pressure parameter of the introduced compressed air is controlled between 0.2 MPa and 0.4 MPa.

9. The molding process according to claim 5, characterized in that, In S4: the blowing and holding time is controlled between 2 and 4 seconds; after being sent into the annealing furnace, stress relief is performed within the temperature range of 550°C to room temperature.

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