Production process of double-color three-dimensional silica gel mark

Abstract

The invention relates to the technical field of silica gel product processing, in particular to a double-color three-dimensional silica gel mark production process which comprises the following steps: step (1), calendaring a first-color silica gel mark layer on first release paper, then hollowing out the first-color silica gel mark layer until the edge roughness Ra is 0.3-0.6 mu m, removing hollowing-out scraps, coating a silane coupling agent solution, standing, and drying the first-color silica gel mark layer to obtain a second-color silica gel mark layer; obtaining a first layer; (2) filling and calendering a second-color silica gel filling layer in the hollow area of the first layer, and then vulcanizing for 4-6 minutes at 145-155 DEG C to obtain a second layer; and (3) in a constant-temperature and constant-humidity environment, a TPU hot melt adhesive film is attached to the surface of the second layer, a second release paper protection layer is attached, and the two-color three-dimensional silica gel mark is obtained. According to the scheme, components are given, and the problem of aging layering of a multi-material composite system is solved synergistically in the aspects of thermodynamics and dynamics through multiple processes; and a double-color three-dimensional effect is obtained through a multi-layer calendering and hollowing technology.

Description

Technical Field

[0001] The present invention relates to the technical field of silicone product processing, and specifically to the production process of two-color three-dimensional silicone logos. Background Art

[0002] With the wide application of silicone products, two-color three-dimensional silicone logos have received extensive attention in the fields of clothing accessories, industrial logos, etc. due to their unique visual effects and functionality. However, the existing production processes of two-color silicone logos still have certain deficiencies in aspects such as the three-dimensional performance of products and the bonding strength between layers, which limit their further promotion and application.

[0003] CN114654644B discloses a production process for multi-color and multi-specification silicone buttons and silicone buttons. This technology realizes the production of multi-color silicone buttons through single-KEY molding and secondary molding processes, which can effectively avoid color mixing phenomena and support combinations of up to 15 colors. However, this technical solution is mainly designed for the planar structure of silicone buttons and does not fully consider the special requirements of three-dimensional logos. Specifically, this process has insufficient optimization of the bonding strength between silicone layers, and problems such as layer separation may occur during long-term use. At the same time, due to the lack of targeted surface treatment processes, the silicone logos produced are prone to fading and aging due to environmental factors (such as ultraviolet rays, high temperatures, etc.), affecting the service life and aesthetics of the products. CN106335153B discloses a production process for silicone pads. This technology realizes the production of double-layer silicone pads through two hot pressing processes, ensuring the flatness and edge softness of the products, and is suitable for scenarios requiring high durability. However, this technical solution is mainly designed for the functional design of silicone pads and does not involve the production process of two-color or multi-color logos. In addition, this process has obvious deficiencies in achieving three-dimensional effects and is difficult to meet the requirements of two-color three-dimensional silicone logos for visual layering. At the same time, due to the lack of special treatment of the silicone surface (such as surface agent coating or debris cleaning), problems such as insufficient surface adhesion may occur in actual applications, thereby affecting the durability and appearance of the logos. Summary of the Invention

[0004] The purpose of the present invention is to provide a production process for two-color three-dimensional silicone logos. By successively processing the first-color silicone logo layer and the second-color silicone filling layer on the first release paper, and combining special surface treatment processes and constant-temperature curing technology, the color stability, anti-aging performance, and bonding strength between layers of the products are significantly improved, while enhancing the visual layering to meet the usage requirements of high-end clothing accessories and industrial logos.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions: A production process for two-color three-dimensional silicone logos, comprising the following steps: Step (1): Calender the first-color silicone identification layer on the first release paper with a thickness of 0.6 - 1.0 mm and a calendering speed of 1.5 - 2.5 m / min; then laser or die-cut and hollow out the first-color silicone identification layer to form a hollowed area with a pattern edge roughness Ra of 0.3 - 0.6 μm, use high-pressure air to blow and remove the hollowed debris, coat with a silane coupling agent solution, and let it stand to obtain the first layer; Step (2): Fill the hollowed area of the first layer with the second-color silicone filling layer by calendering, with a thickness of 0.4 - 0.7 mm, a pressure of 6 - 9 MPa, and a calendering speed of 1.5 - 2.5 m / min; then vulcanize at 145 - 155 °C for 4 - 6 min to obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 20 - 25 °C and a humidity of 35 - 45%, attach a TPU hot melt adhesive film to the surface of the second layer and apply a second release paper protective layer to obtain a two-color three-dimensional silicone identification.

[0006] The first layer (flat calendering): Calender the whole surface on the first release paper, and the silicone flows in a continuous and uniform layer. The pressure has little influence on the thickness control (the thickness is mainly adjusted by the roll gap). The second layer (hollow filling): It is necessary to accurately fill the hollowed area. Insufficient pressure will cause incomplete filling, resulting in bubbles or lack of glue, and excessive pressure will squeeze the first layer and cause deformation. Therefore, the pressure range needs to be limited.

[0007] Preferably, the first release paper is a high-temperature resistant Graffix release paper; the second release paper is Graffix release paper, CCK paper or SCK paper.

[0008] Preferably, the material formula of the first-color silicone identification layer includes: 100 parts by weight of methyl vinyl silicone rubber; 1.5 - 2.5 parts of vulcanizing agent; 6 - 12 parts of inorganic pigment; 1 - 3 parts of anti-aging agent, which may include benzotriazole ultraviolet absorbers.

[0009] Preferably, the material formula of the second-color silicone filling layer includes: 100 parts by weight of methyl vinyl silicone rubber; 1.0 - 1.5 parts of vulcanizing agent; 5 - 8 parts of inorganic pigment; 1 - 2 parts of tackifying resin.

[0010] Preferably, the edge of the hollowed area is a serrated structure.

[0011] Preferably, before coating the silane coupling agent solution, the hollowed surface is treated with argon plasma, with a power of 40 - 60 W and a time of 30 - 60 s.

[0012] After the first - color silica gel layer is treated with argon plasma, the surface is etched and high - density silanol groups (-SiOH) are generated, increasing the surface energy. This activated surface condenses with the silanol groups generated by the hydrolysis of the silane coupling agent (γ - aminopropyltriethoxysilane). The water for this hydrolysis comes from the moisture in the air. This is due to the fact that the silane coupling agent solution contacts the air in a coating manner and absorbs water vapor in the air during the standing process to achieve hydrolysis, and then forms a Si - O - Si covalent bond network. At the same time, the saw - tooth structure produces a mechanical interlocking effect during the calendering and filling of the second - color silica gel: the second - color silica gel thickened with liquid silicone resin penetrates into the saw - tooth gaps under a pressure of 6 - 9 MPa and forms an "inverted hook - type" physical lock after curing. The coupling effect of chemical bonding and mechanical interlocking improves the inter - layer peeling strength and effectively inhibits the internal stress delamination caused by the aging and shrinkage of silica gel.

[0013] Preferably, the first - color silica gel identification layer is pre - vulcanized at 145 - 150 °C for 80 - 100 s before hollowing.

[0014] The process adopts a staged vulcanization strategy: the first layer is partially cross - linked during pre - vulcanization to maintain dimensional stability during subsequent hollowing processing; the final vulcanization after the second - layer filling forms an interpenetrating cross - linked network structure at the interface of the two - color silica gels. The gradient design of the higher cross - link density of the first layer and the lower cross - link density of the second layer reduces the difference in thermal shrinkage rate. Coating with expensive high - temperature - resistant Grafflex release paper plays a key role in this process: its heat resistance of ≥200 °C prevents the migration of silicone during high - temperature vulcanization from polluting the interface; the ultra - flatness of 0.02 mm ensures the uniformity of calendering thickness; the precise peeling force of 0.8 - 1.5 N / cm avoids damaging the weak interface layer between silica gel layers during peeling.

[0015] Preferably, the silane coupling agent solution is a 1 - 3% by mass γ - aminopropyltriethoxysilane ethanol solution.

[0016] Preferably, the TPU hot - melt adhesive film is pre - heated at 75 - 85 °C before lamination, and the lamination pressure is 0.4 - 0.6 MPa.

[0017] Preferably, the basis weight of the Grafflex release paper is 60 - 80 g / m 2 and the silicone oil coating amount is 0.8 - 1.2 g / m 2 .

[0018] In summary, through the unique two - color silica gel layer processing technology, fine surface treatment technology, and strict process parameter control, the present invention has successfully solved the problems of fading, aging, insufficient three - dimensional sense, and easy inter - layer separation existing in the prior art, and has significant technological progress and market application value.

[0019] The present invention has the following advantages: 1. This solution integrates surface energy regulation (plasma activation), interfacial chemical grafting (silane coupling), physical anchoring (serrated structure), and macroscopic stress balance (gradient vulcanization / release paper support), and synergistically solves the problem of aging delamination in multi-material composite systems at the thermodynamic and kinetic levels.

[0020] 2. Through multi-layer calendering and hollowing techniques, a two-color three-dimensional effect is obtained. Detailed implementation manners

[0021] The following specific embodiments illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. General embodiment

[0022] A production process for two-color three-dimensional silicone labels includes the following steps: Step (1): On a high-temperature Graffix release paper with a basis weight of 60 - 80 g / m 2 and a silicone oil coating amount of 0.8 - 1.2 g / m 2 (temperature resistance 210°C, surface flatness 0.01 mm, peel strength 1.3 N / cm), calender the first-color silicone label layer (material formula: 100 parts by weight of methyl vinyl silicone rubber, 2 parts of sulfur powder, 10 parts of iron red powder, 1 part of 2-(2H-benzotriazol-2-yl)-4,6-ditert-amylphenol, and 1 part of pentaerythritol tetra[β-(3,5-ditert-butyl-4-hydroxyphenyl)propionate]), control the thickness to be 0.6 - 1.0 mm, and the calendering speed to be 1.5 - 2.5 m / min; then pre-vulcanize at 145 - 150°C for 80 - 100 s; after vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.3 - 0.6 μm; after purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface (power 40 - 60 W, time 30 - 60 s), and then coat with a 1 - 3% by mass γ-aminopropyltriethoxysilane ethanol solution, and let it stand for 30 min at a temperature of 25°C and a humidity of 60% to obtain the pretreated first layer; Step (2): In the hollow area of the first layer obtained in step (1), fill with a calendered second-color silicone filling layer (material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.0 - 1.5 parts of sulfur powder, 5 - 8 parts of titanium dioxide, 1 - 2 parts of tackifying resin), control the filling thickness to be 0.4 - 0.7 mm, the calendering pressure to be 6 - 9 MPa, and the calendering speed to be 1.5 - 2.5 m / min; then vulcanize the overall structure at 145 - 155 °C for 4 - 6 minutes to complete the crosslinking and compounding of the two-color silicone layer and obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 20 - 25 °C and a humidity of 35 - 45%, after preheating the TPU hot melt adhesive film at 80 °C, cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label. Example 1

[0023] A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature resistant Grains release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender a first-color silicone label layer, control the thickness to be 0.8 mm, and the calendering speed to be 2.0 m / min; then pre-vulcanize at 148 °C for 90 s; after vulcanization, perform laser hollowing processing to form a hollow area with a serrated structure at the edge and a roughness Ra of 0.5 μm; after purging the debris with high-pressure air, perform argon plasma treatment on the hollow surface with a power of 50 W and a time of 45 s, then coat with a 2% by mass γ-aminopropyltriethoxysilane ethanol solution and let it stand for 30 min under the conditions of a temperature of 25 °C and a humidity of 60% to obtain a pretreated first layer; Step (2): In the hollow area of the first layer obtained in step (1), fill with a calendered second-color silicone filling layer, material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, 1.5 parts of tackifying resin; control the filling thickness to be 0.6 mm, the calendering pressure to be 8 MPa, and the calendering speed to be 2.0 m / min; then vulcanize the overall structure at 150 °C for 5 minutes to complete the crosslinking and compounding of the two-color silicone layer and obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, after preheating the TPU hot melt adhesive film at 80 °C, cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label. Example 2

[0024] A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature resistant Grains release paper with a basis weight of 80 g / m 2, silicone oil coating amount 1.2 g / m 2 On a high-temperature resistant Graffix release paper with a silicone oil coating amount of 1.2 g / m², calender the first-color silicone identification layer, controlling the thickness at 1.0 mm and the calendering speed at 2.5 m / min; then pre-vulcanize at 150 °C for 100 s; after vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a surface roughness Ra of 0.3 μm; after removing debris by blowing with high-pressure air, perform argon plasma treatment on the hollowed surface at 45 W for 40 s, then coat with a 1.5% by mass γ-aminopropyltriethoxysilane ethanol solution, and let it stand for 30 min at a temperature of 25 °C and a humidity of 60% to obtain the pretreated first layer; Step (2): In the hollowed area of the first layer obtained in step (1), fill with a calendered second-color silicone filling layer. The material formula is: 100 parts by weight of methyl vinyl silicone rubber, 1.5 parts of sulfur powder, 8 parts of titanium dioxide, and 2 parts of tackifying resin. Control the filling thickness at 0.7 mm, the calendering pressure at 9 MPa, and the calendering speed at 1.5 m / min; then vulcanize the overall structure at 155 °C for 6 minutes to complete the cross-linking and compounding of the two-color silicone layer and obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80 °C and then cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone identification.

[0025] Comparative Example 1 The difference from Example 1 is that the first-color silicone identification layer is not pre-vulcanized: A production process for a two-color three-dimensional silicone identification, comprising the following steps: Step (1): On a high-temperature resistant Graffix release paper with a basis weight of 70 g / m² 2 , silicone oil coating amount 1.0 g / m 2 ², calender the first-color silicone identification layer, controlling the thickness at 0.8 mm and the calendering speed at 2.0 m / min; then perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a surface roughness Ra of 0.5 μm; after removing debris by blowing with high-pressure air, perform argon plasma treatment on the hollowed surface at a power of 50 W for 45 s, then coat with a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and let it stand for 30 min at a temperature of 25 °C and a humidity of 60% to obtain the pretreated first layer; Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer. The material formula is as follows: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin. Control the filling thickness at 0.6 mm, the calendering pressure at 8 MPa, and the calendering speed at 2.0 m / min. Then vulcanize the overall structure at 150°C for 5 minutes to complete the crosslinking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23°C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80°C and then cover it on the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0026] Comparative Example 2 The difference from Example 1 is that the roughness Ra of the hollowed part is 0.2 μm: A production process for a two-color three-dimensional silicone label includes the following steps: Step (1): On a high-temperature resistant Grafflex release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender a first-color silicone label layer, control the thickness at 0.8 mm, and the calendering speed at 2.0 m / min. Then pre-vulcanize at 148°C for 90 s. After vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.2 μm. After purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface with a power of 50 W and a time of 45 s, then coat a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and let it stand for 30 min under the conditions of a temperature of 25°C and a humidity of 60% to obtain a pretreated first layer. Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer. The material formula is as follows: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin. Control the filling thickness at 0.6 mm, the calendering pressure at 8 MPa, and the calendering speed at 2.0 m / min. Then vulcanize the overall structure at 150°C for 5 minutes to complete the crosslinking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23°C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80°C and then cover it on the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0027] Comparative Example 3 The difference from Example 1 is that the roughness Ra of the hollowed part is 0.8 μm: A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature-resistant Grafoil release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender the first-color silicone label layer, controlling the thickness at 0.8 mm and the calendering speed at 2.0 m / min; then pre-vulcanize at 148 °C for 90 s; after vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.8 μm; after purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface, with a power of 50 W and a time of 45 s, then coat with a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and let stand for 30 min under the conditions of a temperature of 25 °C and a humidity of 60% to obtain the pre-treated first layer; Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender the second-color silicone filling layer, with the material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin; control the filling thickness at 0.6 mm, the calendering pressure at 8 MPa, and the calendering speed at 2.0 m / min; then vulcanize the overall structure at 150 °C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer and obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, after preheating the TPU hot-melt adhesive film at 80 °C, cover it onto the surface of the second layer in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain the two-color three-dimensional silicone label.

[0028] Comparative Example 4 The difference from Example 1 is that the hollowed area is not subjected to plasma treatment: A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature-resistant Grafoil release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender the first-color silicone label layer, controlling the thickness at 0.8 mm and the calendering speed at 2.0 m / min; then pre-vulcanize at 148 °C for 90 s; after vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.5 μm; after purging debris with high-pressure air, coat with a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and let stand for 30 min under the conditions of a temperature of 25 °C and a humidity of 60% to obtain the pre-treated first layer; Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer. The material formula is: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin. Control the filling thickness to be 0.6 mm, the calendering pressure to be 8 MPa, and the calendering speed to be 2.0 m / min. Then vulcanize the overall structure at 150 °C for 5 minutes to complete the crosslinking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80 °C and then cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0029] Comparative Example 5 The difference from Example 1 is that the plasma treatment parameters at the hollowed part are too large: A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature resistant Grafflex release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender a first-color silicone label layer, control the thickness to be 0.8 mm, and the calendering speed to be 2.0 m / min. Then pre-vulcanize at 148 °C for 90 s. After vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.5 μm. After purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface with a power of 120 W and a time of 90 s, and then coat a 2% by mass γ-aminopropyltriethoxysilane ethanol solution. Let it stand for 30 min under the conditions of a temperature of 25 °C and a humidity of 60% to obtain a pretreated first layer. Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer. The material formula is: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin. Control the filling thickness to be 0.6 mm, the calendering pressure to be 8 MPa, and the calendering speed to be 2.0 m / min. Then vulcanize the overall structure at 150 °C for 5 minutes to complete the crosslinking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80 °C and then cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0030] Comparative Example 6 The difference from Example 1 is that no silane coupling agent is coated at the hollowed part: A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature-resistant Grafflex release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender the first-color silicone label layer, controlling the thickness to be 0.8 mm and the calendering speed to be 2.0 m / min; then pre-vulcanize at 148 °C for 90 s; after vulcanization, perform laser hollowing processing to form a hollowed-out area with a serrated structure at the edge and a surface roughness Ra of 0.5 μm; after removing debris by blowing with high-pressure air, perform argon plasma treatment on the hollowed-out surface, with a power of 50 W and a time of 45 s, and leave it standing for 30 min under the conditions of a temperature of 25 °C and a humidity of 60% to obtain the pretreated first layer; Step (2): In the hollowed-out area of the first layer obtained in step (1), fill and calender the second-color silicone filling layer, with the material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin; control the filling thickness to be 0.6 mm, the calendering pressure to be 8 MPa, and the calendering speed to be 2.0 m / min; then vulcanize the overall structure at 150 °C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer and obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, after preheating the TPU hot melt adhesive film at 80 °C, cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain the two-color three-dimensional silicone label.

[0031] Comparative Example 7 The difference from Example 1 lies in that the material formula of the second-color silicone filling layer is different: A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature-resistant Grafflex release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender the first-color silicone label layer, controlling the thickness to be 0.8 mm and the calendering speed to be 2.0 m / min; then pre-vulcanize at 148 °C for 90 s; after vulcanization, perform laser hollowing processing to form a hollowed-out area with a serrated structure at the edge and a surface roughness Ra of 0.5 μm; after removing debris by blowing with high-pressure air, perform argon plasma treatment on the hollowed-out surface, with a power of 50 W and a time of 45 s, and then coat a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and leave it standing for 30 min under the conditions of a temperature of 25 °C and a humidity of 60% to obtain the pretreated first layer; Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer with the following material formula: 100 parts by weight of methyl vinyl silicone rubber, 2 parts of sulfur powder, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin. Control the filling thickness at 0.6 mm, the calendering pressure at 8 MPa, and the calendering speed at 2.0 m / min. Then vulcanize the overall structure at 150°C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23°C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80°C and then cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0032] Comparative Example 8 The difference from Example 1 is that the material formula of the second-color silicone filling layer is different: A production process for a two-color three-dimensional silicone label includes the following steps: Step (1): On a high-temperature resistant Grafflex release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender a first-color silicone label layer, control the thickness at 0.8 mm, and the calendering speed at 2.0 m / min. Then pre-vulcanize at 148°C for 90 s. After vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.5 μm. After purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface with a power of 50 W and a time of 45 s, and then coat a 2% by mass γ-aminopropyltriethoxysilane ethanol solution. Let it stand for 30 min under the conditions of a temperature of 25°C and a humidity of 60% to obtain a pretreated first layer. Step (2): In the hollowed area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer with the following material formula: 100 parts by weight of methyl vinyl silicone rubber, 7 parts of titanium dioxide, and 1.5 parts of tackifying resin. Control the filling thickness at 0.6 mm, the calendering pressure at 8 MPa, and the calendering speed at 2.0 m / min. Then vulcanize the overall structure at 150°C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23°C and a humidity of 40%, preheat the TPU hot melt adhesive film at 80°C and then cover it onto the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa. At the same time, apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0033] Comparative Example 9 The difference from Example 1 is that the calendering parameters in step (2) are different: A production process for a two-color three-dimensional silicone label includes the following steps: Step (1): On a high-temperature resistant Graffix release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender the first-color silicone identification layer, controlling the thickness at 0.8 mm and the calendering speed at 2.0 m / min; then pre-vulcanize at 148°C for 90 s; after vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.5 μm; after purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface, with a power of 50 W and a time of 45 s, and then coat with a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and let it stand for 30 min under the conditions of a temperature of 25°C and a humidity of 60% to obtain the pretreated first layer; Step (2): Fill the hollowed area of the first layer obtained in step (1) with a calendered second-color silicone filling layer, and the material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, 1.5 parts of tackifying resin; control the filling thickness at 0.6 mm, the calendering pressure at 15 MPa, and the calendering speed at 1.0 m / min; then vulcanize the overall structure at 150°C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer, and obtain the second layer; Step (3): In a constant temperature and humidity environment with a temperature of 23°C and a humidity of 40%, after preheating the TPU hot melt adhesive film at 80°C, cover it on the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone identification.

[0034] Comparative Example 10 The difference from Example 1 lies in that in step (3), the constant temperature and humidity conditions are different: A production process for a two-color three-dimensional silicone identification, comprising the following steps: Step (1): On a high-temperature resistant Graffix release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender the first-color silicone identification layer, controlling the thickness at 0.8 mm and the calendering speed at 2.0 m / min; then pre-vulcanize at 148°C for 90 s; after vulcanization, perform laser hollowing processing to form a hollowed area with a serrated structure at the edge and a roughness Ra of 0.5 μm; after purging debris with high-pressure air, perform argon plasma treatment on the hollowed surface, with a power of 50 W and a time of 45 s, and then coat with a 2% by mass γ-aminopropyltriethoxysilane ethanol solution, and let it stand for 30 min under the conditions of a temperature of 25°C and a humidity of 60% to obtain the pretreated first layer; Step (2): In the hollow area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer. Material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, 1.5 parts of tackifying resin; control the filling thickness to be 0.6 mm, the calendering pressure to be 8 MPa, and the calendering speed to be 2.0 m / min; then vulcanize the overall structure at 150 °C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 30 °C and a humidity of 50%, after preheating the TPU hot melt adhesive film at 80 °C, cover it on the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0035] Comparative Example 11 The difference from Example 1 is that no standing treatment is performed after coating the silane coupling agent: A production process for a two-color three-dimensional silicone label, comprising the following steps: Step (1): On a high-temperature-resistant Grafflex release paper with a basis weight of 70 g / m 2 and a silicone oil coating amount of 1.0 g / m 2 , calender a first-color silicone label layer, control the thickness to be 0.8 mm, and the calendering speed to be 2.0 m / min; then pre-vulcanize at 148 °C for 90 s; after vulcanization, perform laser hollowing processing to form a hollow area with a serrated structure at the edge and a roughness Ra of 0.5 μm; after purging debris with high-pressure air, perform argon plasma treatment on the hollow surface with a power of 50 W and a time of 45 s, and then coat a 2% by mass ethanol solution of γ-aminopropyltriethoxysilane to obtain a pretreated first layer. Step (2): In the hollow area of the first layer obtained in step (1), fill and calender a second-color silicone filling layer. Material formula: 100 parts by weight of methyl vinyl silicone rubber, 1.3 parts of sulfur powder, 7 parts of titanium dioxide, 1.5 parts of tackifying resin; control the filling thickness to be 0.6 mm, the calendering pressure to be 8 MPa, and the calendering speed to be 2.0 m / min; then vulcanize the overall structure at 150 °C for 5 minutes to complete the cross-linking and compounding of the two-color silicone layer, and obtain the second layer. Step (3): In a constant temperature and humidity environment with a temperature of 23 °C and a humidity of 40%, after preheating the TPU hot melt adhesive film at 80 °C, cover it on the surface of the second layer obtained in step (2) with a laminating pressure of 0.5 MPa, and at the same time apply an SCK paper protective layer to finally obtain a two-color three-dimensional silicone label.

[0036] The effect detection is shown in Table 1.

[0037] Table 1:

[0038] In Comparative Example 1 compared with Example 1, the first-color silica gel identification layer was not pre-vulcanized and lacked pre-crosslinking. Uncontrolled flow deformation occurred during the calendering of the filling layer, resulting in a complete collapse of the structure. At the same time, the uncured interface relied only on weak physical adsorption, and the subsequent vulcanization process caused the migration of iron oxide red pigment.

[0039] In Comparative Example 2 compared with Example 1, the surface of the hollowed-out part was overly smooth, and the mechanical interlocking area was reduced by 65%, significantly weakening the interfacial bonding force and intensifying interfacial slippage during thermal cycling.

[0040] In Comparative Example 3 compared with Example 1, the hollowed-out part was too rough, resulting in stress concentration and causing local debonding.

[0041] In Comparative Example 4 compared with Example 1, the hollowed-out part was not treated with plasma. The silica gel at the hollowed-out part had low activity, and silane could not be effectively bonded. The lack of chemical bonds caused the interfacial peel strength to plummet, and the thermal expansion mismatch could not be compensated.

[0042] In Comparative Example 5 compared with Example 1, the plasma treatment at the hollowed-out part was excessive, and local high temperature might have caused surface carbonization, forming a weak boundary layer.

[0043] In Comparative Example 6 compared with Example 1, the hollowed-out part was not treated with silane coupling agent, relying only on van der Waals forces. The peel force decreased sharply, and the delamination rate during thermal cycling was high.

[0044] In Comparative Example 7 compared with Example 1, the sulfur content in the second-color rubber filling layer was excessive, resulting in stress concentration caused by curing shrinkage and inducing microcracks. Excessive sulfur also oxidized titanium dioxide white pigment, causing yellowing.

[0045] In Comparative Example 8 compared with Example 1, there was no sulfur in the second-color rubber filling layer, resulting in non-crosslinking. The difference in thermal expansion coefficients was large, and the interface was torn under thermal stress. The non-crosslinked structure lost its strength.

[0046] In Comparative Example 9 compared with Example 1, step (2) was carried out under high-pressure calendering, resulting in internal stress concentration, weakening the interlayer bonding, and inducing the expansion of interface gaps.

[0047] In Comparative Example 10 compared with Example 1, the humidity was too high, resulting in hindered molecular diffusion during the TPU lamination. The delamination risk was still significant in the humid and hot environment.

[0048] In Comparative Example 11 compared with Example 1, no static treatment was carried out after coating the silane coupling agent, resulting in incomplete hydrolysis of the coupling agent and a sharp reduction in the peel force. The delamination rate during thermal cycling was high.

[0049] In summary, through pre-vulcanization structure shaping, plasma precise activation, silane chemical bonding, and sulfur gradient control, the Example achieved a dual "mechanical-chemical" locking at the interface, with high peel force, and leading comprehensively in thermal expansion matching and color stability.

Claims

1. A production process for a two-color three-dimensional silicone logo, characterized in that, It includes the following steps: Step (1): Calender a first-color silicone identification layer on a first release paper, then perforate the first-color silicone identification layer, with the edge roughness Ra being 0.3 - 0.6 μm, remove the perforation debris, coat with a silane coupling agent solution, and let it stand to obtain the first layer; Step (2): Fill the perforated area of the first layer with a calendered second-color silicone filling layer, then vulcanize at 145 - 155 °C for 4 - 6 min to obtain the second layer; Step (3): In a constant temperature and humidity environment, with the temperature at 20 - 25 °C and the humidity at 35 - 45%, attach a TPU hot melt adhesive film to the surface of the second layer, and apply a second release paper protective layer to obtain a two-color three-dimensional silicone identification.

2. The production process of the two-color three-dimensional silicone label as described in claim 1, characterized in that, Calender a first-color silicone identification layer on the first release paper, with the calendering speed being 1.5 - 2.5 m / min.

3. The production process of the two-color three-dimensional silicone label as described in claim 1, wherein, Fill the perforated area of the first layer with a calendered second-color silicone filling layer, with the pressure being 6 - 9 MPa and the calendering speed being 1.5 - 2.5 m / min; the edge of the perforated area is a serrated structure.

4. The production process of the two-color three-dimensional silicone label according to claim 1, characterized in that, The first release paper is a high-temperature resistant Glassine release paper with a basis weight of 60-80 g / m 2 and a silicone oil coating amount of 0.8-1.2 g / m 2 ; The second release paper is Glassine release paper, CCK paper or SCK paper.

5. The production process of the two-color three-dimensional silicone logo according to claim 1, characterized in that, The material formula of the first-color silicone identification layer includes: 100 parts by weight of methyl vinyl silicone rubber; 1.5 - 2.5 parts of vulcanizing agent; 6 - 12 parts of inorganic pigment; 1 - 3 parts of anti-aging aid.

6. The production process of the two-color three-dimensional silicone label according to claim 1, characterized in that, The material formula of the second-color silicone filling layer includes: 100 parts by weight of methyl vinyl silicone rubber; 1.0 - 1.5 parts of vulcanizing agent; 5 - 8 parts of inorganic pigment; 1 - 2 parts of tackifying resin.

7. The production process of the two-color three-dimensional silicone logo according to claim 1, characterized in that The TPU hot melt adhesive film is preheated at 75 - 85 °C before attachment, and the attachment pressure is 0.4 - 0.6 MPa.

8. The production process of the two-color three-dimensional silicone logo according to claim 1, characterized in that, Before coating the silane coupling agent solution, the perforated surface is treated with argon plasma, with the power being 40 - 60 W and the time being 30 - 60 s.

9. The production process of the two-color three-dimensional silicone logo according to claim 1, characterized in that, The first-color silicone identification layer is pre-vulcanized at 145 - 150 °C for 80 - 100 s before perforation.

10. The production process of the two-color three-dimensional silicone label as described in claim 1, characterized in that, The silane coupling agent solution is a 1 - 3% by mass γ-aminopropyltriethoxysilane ethanol solution.

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