High performance decorative laminated glass with ultraviolet printed images and method of making the same

Abstract

The present application relates to the technical field of decorative laminated material, and particularly relates to high-performance decorative laminated glass with ultraviolet printed image and a preparation method thereof. The laminated glass comprises outer glass, first adhesive layer, printed composite layer, second adhesive layer and inner glass which are sequentially stacked; the printed composite layer comprises polymer support film, UV printed image layer and polymer film; the UV printed image layer is printed on the polymer support film by UV curing ink and is clamped between the polymer support film and the polymer film; the polymer film is selected from thermoplastic polyurethane film or ethylene-vinyl acetate copolymer film. The present application forms sandwich structure by clamping the UV printed image layer between the polymer support film and the polymer film, and combines two-step curing process of partial curing and complete curing, so that the interlayer adhesion and impact resistance are significantly improved.

Description

Technical Field

[0001] This invention relates to the field of decorative laminated materials technology, and in particular to a high-performance decorative laminated glass with ultraviolet printed images and its preparation method. Background Technology

[0002] Laminated glass, as a safety composite material, is widely used in building curtain walls, automobile windows, furniture decoration, and other fields. It is usually made by laminating two or more layers of glass with a polymer adhesive layer (such as polyvinyl butyral PVB, ethylene-vinyl acetate copolymer EVA, etc.) under high temperature and pressure, and has the safety characteristic of not shattering into pieces.

[0003] With the increasing market demand for decorative finishes, the industry is committed to introducing patterned printing into laminated glass. Traditional decorative methods mainly rely on screen printing or ceramic enamel glass. However, these technologies have significant drawbacks: screen printing has long preparation times, high costs for small-batch production, and poor pattern flexibility; while ceramic enamel glass, although capable of achieving certain pattern effects, undergoes physicochemical reactions with the glass substrate during high-temperature processing, significantly reducing the local strength of the glass and resulting in a substantial decrease in the impact resistance of the laminate, making it difficult to meet safety requirements such as wind pressure resistance in buildings or gravel impact resistance in automobiles.

[0004] To overcome the aforementioned shortcomings, digital printing technology, especially ultraviolet (UV) curable ink printing, has been attempted to be introduced into the laminated glass industry. UV curable inks offer advantages such as fast curing speed (1-3 seconds), no volatile organic compound (VOC) emissions, vibrant colors, and high resolution, meeting the needs of small-batch, personalized customization, and avoiding the damage to glass strength caused by ceramic materials. Therefore, UV curable inks are considered an ideal alternative to traditional decorative methods.

[0005] However, in the practical application of combining UV-cured ink with laminated glass technology, the following key technical bottlenecks still exist: (1) Insufficient adhesion: After conventional complete curing, UV ink forms a highly cross-linked and dense surface layer with low surface energy, making it difficult to form an effective interface bond with the glass substrate or PVB and other adhesive layers. When the laminated glass is subjected to shear force or impact, the printed layer is prone to interface peeling, resulting in significant hidden dangers in the product's service life and safety; (2) Poor interlayer compatibility: The introduction of UV ink layer destroys the homogeneous interface structure of "glass-adhesive layer-glass" in traditional laminated glass. Due to the mismatch between the polarity or rheological properties of the ink composition and the adhesive layer material, micro-voids or poor bonding are easily generated during the lamination process, affecting the overall optical transparency (such as increased haze) and interlayer bonding strength; (3) Low functional integration: In the existing technology, if functional particles are added to the ink to achieve functions such as invisible patterns or infrared blocking in non-illuminated states, it often further deteriorates the ink's adhesion or interlayer bonding performance, lacking a systematic integrated design of the materials and functions of each layer.

[0006] Therefore, how to achieve a high degree of freedom in decorative effects using UV-cured inks while overcoming the adhesion and compatibility defects between them and laminated glass structures, and obtaining mechanical properties that meet safety standards, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] The purpose of this invention is to address the problems existing in the prior art by providing a high-performance decorative laminated glass with ultraviolet printed images and its preparation method. By sandwiching a UV printed image layer between a polymer support film and a polymer film to form a sandwich structure, and combining a two-step curing process of partial curing and full curing, the interlayer adhesion and impact resistance are significantly improved.

[0008] To achieve the above objectives, the present invention provides a high-performance decorative laminated glass with a UV-printed image, comprising an outer glass layer, a first adhesive layer, a printed composite layer, a second adhesive layer, and an inner glass layer stacked sequentially; the printed composite layer comprises a polymer support film, a UV-printed image layer, and a polymer film; the UV-printed image layer is formed on the polymer support film by UV-curable ink printing and sandwiched between the polymer support film and the polymer film; The polymer film is selected from thermoplastic polyurethane (TPU) film or ethylene-vinyl acetate copolymer (EVA) film.

[0009] In an optional embodiment, when the polymer film is a TPU film, the molecular weight of the TPU is 80,000-150,000; when the polymer film is an EVA film, the melt index of the EVA is 5-15 g / 10 min.

[0010] In the decorative laminated glass provided by the present invention, the polymer support film and the polymer film together encapsulate the UV printed image layer, forming a sandwich structure. This not only provides physical protection and isolation for the image layer, preventing it from interacting adversely with the adhesive layer during the lamination process, but also enhances the interfacial bonding force between the printed composite layer and the adhesive layers on both sides.

[0011] In one optional embodiment, the outer glass layer has a thickness of 1.5-3 mm, the inner glass layer has a thickness of 0.05-1.2 mm, and the thickness ratio of the outer glass layer to the inner glass layer is 1.25-30.

[0012] In one optional embodiment, the outer glass layer is selected from unstrengthened glass (glass that has not undergone any strengthening treatment after leaving the factory), annealed glass, or heat-strengthened glass; the inner glass layer is chemically strengthened glass, for example, by ion exchange treatment of the glass in a potassium nitrate solution to form a compressive stress layer on its surface. Specifically, the surface compressive stress of the inner glass layer is ≥200MPa, and the compressive stress layer depth is ≥10μm, wherein the compressive stress layer depth refers to the thickness of the layer with compressive stress extending from the glass surface inward.

[0013] By using chemically strengthened glass as the inner layer and achieving a reasonable thickness match with the outer glass, laminated glass can achieve excellent impact resistance while maintaining good optical performance.

[0014] In an optional embodiment, the polymer support film is selected from polyvinyl butyral (PVB) film, polyethylene terephthalate (PET) film, or ethylene-vinyl acetate copolymer (EVA) film.

[0015] In an optional embodiment, when the polymer support film is a PVB film, the PVB film contains PVB and a plasticizer; the hydroxyl content of PVB is 10-35wt%, the residual ester group content is <15wt%, and the molecular weight is ≥30000g / mol; the plasticizer is selected from triethylene glycol diisooctanoate, and the content of plasticizer in the PVB film is 5-45wt%.

[0016] In an optional embodiment, when the polymer support film is a PET film with a molecular weight of 20,000-25,000 g / mol, the PET film is preferably subjected to biaxial stretching and heat stabilization treatment so that its biaxial shrinkage rate after exposure at 150°C for 30 min is <2%, in order to ensure good dimensional stability during the lamination process.

[0017] In an optional embodiment, when the polymer support film is an EVA film, the melt index of EVA is 5-15 g / 10 min.

[0018] In one optional embodiment, the viscosity of the UV-curable ink is 1-50 mPa·s (measured at 25°C).

[0019] In an optional embodiment, the UV-curable ink comprises a polymerizable monomer selected from 1,6-hexanediol diacrylate (HDDA).

[0020] In an optional embodiment, the UV-curable ink further includes scattering particles; the scattering particles are selected from at least one of TiO2, SiO2, CaCO3, ZnO, Al2O3, and ZrO2; the D90 of the scattering particles is < 2 μm; and the mass ratio of the polymerizable monomer to the scattering particles is (50-99):(0.05-20). By adding appropriate types and amounts of scattering particles, specific optical effects can be achieved while maintaining pattern clarity, such as making the pattern invisible in non-illuminated conditions, thereby meeting the needs of different decorative scenarios for optical scattering or visual effects.

[0021] In an optional embodiment, the UV-curable ink further includes a photoinitiator, a leveling agent, and a thermoplastic polymer material; the mass ratio of the polymerizable monomer, photoinitiator, leveling agent, and thermoplastic polymer material is (50-99):(0.01-20):(0.01-20):(0.1-20).

[0022] In an optional embodiment, the photoinitiator is selected from 2-hydroxy-2-methyl-1-phenylpropanone; the leveling agent is selected from polyacrylate leveling agents (BYK-354).

[0023] In one optional embodiment, the thermoplastic polymer material is selected from at least one of polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), and ionomers.

[0024] In an optional embodiment, when the thermoplastic polymer material is PVB, the PVB has a hydroxyl content of 10-35 wt%, a residual ester content of <15 wt%, and a molecular weight of ≥30000 g / mol; the PVB contains a plasticizer selected from triethylene glycol diisooctanoate; and the plasticizer content is 5-45 wt% based on the total mass of the PVB containing the plasticizer.

[0025] In an optional embodiment, when the thermoplastic polymer material is EVA, the melt index of EVA is 5-15 g / 10 min.

[0026] In an optional embodiment, when the thermoplastic polymer material is TPU, the molecular weight of TPU is 80,000-150,000.

[0027] In an optional embodiment, to improve the dispersion uniformity of the thermoplastic polymer material, it can be pre-dissolved in an organic solvent and added to the ink system in solution form. The organic solvent is selected from at least one of alcohol solvents and ether solvents, and evaporates during printing and curing. By adding the thermoplastic polymer material to the UV-curable ink, the compatibility between the ink and the polymer support film and polymer film can be improved, further enhancing interlayer adhesion.

[0028] In an optional embodiment, the thickness ratio of the polymer film to the polymer support film is ≤1 / 2.

[0029] In one optional embodiment, the materials of the first adhesive layer and the second adhesive layer are selected from polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), or ionomers, respectively.

[0030] In an optional embodiment, when the first and second adhesive layers are made of PVB (i.e., when the first and second adhesive layers are PVB films), the PVB film contains PVB and a plasticizer; the PVB has a hydroxyl content of 10-35 wt%, a residual ester content of <15 wt%, and a molecular weight of ≥30000 g / mol to ensure good adhesion performance and optical transparency. The plasticizer is selected from triethylene glycol diisooctanoate; the glass transition temperature (Tg) of the PVB film can be adjusted according to the plasticizer content, and the Tg is preferably 20-30°C to match the lamination process conditions and obtain suitable flexibility.

[0031] In an optional embodiment, when the first adhesive layer and the second adhesive layer are made of TPU, the molecular weight of the TPU is 80,000-150,000.

[0032] In an optional embodiment, when the first adhesive layer and the second adhesive layer are made of EVA film, the melt index of EVA is 5-15 g / 10 min.

[0033] The present invention also provides a method for preparing the high-performance decorative laminated glass with ultraviolet printed images, comprising the following steps: S1. UV-curable ink is printed onto the surface of the polymer support film, and a first curing is performed to obtain the printed polymer support film; S2. Composite the polymer film with the printed polymer support film, so that the UV printed image layer is located between the polymer support film and the polymer film, and perform a second curing to obtain the printed composite layer; S3. The outer glass, the first adhesive layer, the printed composite layer, the second adhesive layer and the inner glass are stacked in that order and pressed to obtain a high-performance decorative laminated glass with an ultraviolet printed image.

[0034] In the preparation method provided by this invention, a two-step curing process of "partial curing (first curing) - lamination - complete curing (second curing)" is adopted. That is, the first curing uses a low power to keep the UV ink in a partially cross-linked state, and the second complete curing is carried out after lamination with the polymer film. This process can effectively avoid the problem of poor interfacial bonding between the dense surface layer formed after the UV ink is fully cured and the subsequent layers, and significantly improve the adhesion between the UV printed image layer and the polymer support film and the polymer film.

[0035] In an optional embodiment, in S1, prior to printing, the polymer support film undergoes a surface treatment to increase its surface tension to above 0.035 N / m. The surface treatment is selected from at least one of corona discharge, flame treatment, and plasma treatment.

[0036] In an optional implementation, in S1, the power of the first curing UV lamp is 30-50%, and the curing time is 1-2 seconds.

[0037] In an optional embodiment, in S2, the temperature of the composite is 60-80°C and the pressure is 0.3-0.5 MPa; the power of the second curing UV lamp is 80-100% and the time is 2-3 seconds.

[0038] In an optional embodiment, in S3, before pressing, the laminated body is pre-pressed to expel interlayer air and achieve temporary bonding. The pre-pressing process can be carried out in a manner conventional in the art, such as sequential processing with a room temperature pressure roller and a heated pressure roller, or a combination of processing with a room temperature pressure roller, heating, and re-pressurization.

[0039] In an optional embodiment, in S3, the pressing temperature is 130-150°C and the pressure is 1050-1275 kN / m. 2 The pressing time is 30-90 minutes. After pressing, the laminated glass can be trimmed, cleaned, and its performance tested as needed.

[0040] The present invention has achieved the following beneficial effects: (1) This invention forms a sandwich structure of "support film-image layer-film" by placing the UV-printed image layer between the polymer support film and the polymer film. The preparation process employs a two-step curing process of "partial curing (first curing) - lamination - complete curing (second curing)," effectively avoiding the interfacial bonding problems caused by the formation of a dense surface layer after complete curing of the UV ink. The polymer support film and the polymer film together encapsulate the UV-printed image layer, providing physical protection and isolation, preventing adverse interactions between the image layer and the adhesive layer during lamination, and simultaneously enhancing the interfacial bonding between the printed composite layer and the adhesive layers on both sides. Test results show that the compressive shear strength of the embodiments of this invention reaches over 7 MPa, far superior to the comparative example (<1 MPa), significantly improving the interlayer adhesion and structural stability of the laminated glass.

[0041] (2) This invention uses chemically strengthened glass as the inner layer, with a surface compressive stress ≥200MPa and a compressive stress layer depth ≥10μm, forming a reasonable thickness match with the outer layer glass (selected from unstrengthened, annealed, or heat-strengthened glass) with a thickness of 1.5-3mm (the thickness ratio of the outer layer to the inner layer is 1.25-30). This structural design enables the laminated glass to achieve excellent impact resistance while maintaining good optical performance. The stone impact resistance test results show that the fracture rate of the embodiment of this invention is 40%-55% in the speed range of 75-85 mph, which is much lower than the 90% or more of the comparative example, and can meet the safety requirements of wind pressure resistance in buildings and stone impact resistance in automobiles.

[0042] (3) In the embodiments of the present invention, the laminated glass without added scattering particles has a light transmittance of ≥90% and a haze of ≤0.52%, maintaining excellent optical transparency and suitable for application scenarios with high transparency requirements. By adding scattering particles to the UV-cured ink, the printed pattern can achieve an invisible effect in non-illuminated conditions, while the light transmittance can be adjusted to approximately 80% and the haze increased to over 22%, meeting the functional requirements of specific decorative scenarios (such as building curtain walls, privacy protection, etc.). This adjustability of optical performance gives the product of the present invention a wider range of application prospects.

[0043] (4) By adding thermoplastic polymer materials to UV-curable inks, and optionally dissolving them in an organic solvent before adding them to the ink system, the present invention significantly improves the compatibility between the ink and the polymer support film and the polymer film, avoiding the problems of microscopic voids or poor bonding during the lamination process. Test results show that the optical performance of the embodiments of the present invention is stable, and no abnormal increase in haze or significant decrease in light transmittance has been observed.

[0044] (5) The UV-curable ink used in this invention does not contain volatile organic compounds (VOCs), has a fast curing speed, does not require a lengthy drying process, meets environmental protection requirements, and has high production efficiency. The preparation process is compatible with digital printing technologies such as inkjet printing, and has a short preparation time, low cost, and fast turnaround time for small-batch production. It is suitable for personalized customization needs and has good prospects. Detailed Implementation

[0045] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0046] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0047] Example 1 This embodiment provides a high-performance decorative laminated glass with ultraviolet printed images and a method for preparing the same.

[0048] 1. Raw material preparation (1) Glass substrate Outer glass: Annealed soda-lime glass with a thickness of 2.1 mm is selected (the soda-lime glass is held at 530℃ for 45 min; then slowly cooled to 400℃ at a rate of 2℃ / min, and then accelerated to room temperature at a rate of 4℃ / min to ensure that the internal stress of the glass is fully eliminated, thus obtaining annealed soda-lime glass).

[0049] Inner glass: Chemically strengthened aluminosilicate glass with a thickness of 0.7 mm is selected (aluminosilicate glass is placed in potassium nitrate solution for ion exchange treatment to form a compressive stress layer on its surface to obtain chemically strengthened aluminosilicate glass). Specifically, its surface compressive stress is 600 MPa and the depth of the compressive stress layer is 100 μm.

[0050] (2) Polymer-supported membrane A 0.254 mm thick PVB film was selected. The PVB film contains PVB and a plasticizer. The hydroxyl content of PVB is 25 wt%, the residual ester content is 3 wt%, and the molecular weight is 60000 g / mol. The plasticizer is triethylene glycol diisooctanoate, and the plasticizer content in the PVB film is 30 wt%.

[0051] (3) UV-curable ink (based on a total mass of 100wt%) Polymerizable monomer (HDDA) 80wt%, scattering particles (TiO2, D90 0.4μm) 0.2wt%, photoinitiator (2-hydroxy-2-methyl-1-phenylpropanone) 3.5wt%, polyacrylate leveling agent (BYK-354) 0.3wt%, thermoplastic polymer material (PVB, PVB with 25wt% hydroxyl content, 3wt% residual ester content, and molecular weight of 60000g / mol; PVB contains plasticizer, which is triethylene glycol diisooctanoate, and the plasticizer content is 30wt% based on the total mass of PVB containing plasticizer) 16wt%.

[0052] The thermoplastic polymer material was pre-dissolved in an organic solvent (ethanol and dipropylene glycol methyl ether, volume ratio 1:1). It was then mixed thoroughly with the remaining components, controlling the viscosity to 7 mPa·s (at 25°C).

[0053] (4) Polymer film A TPU film with a thickness of 0.127 mm (the molecular weight of TPU is 110,000) was selected.

[0054] (5) Adhesive layer Both the first and second adhesive layers are made of PVB film with a thickness of 0.38 mm. The PVB film contains PVB and plasticizer. The hydroxyl content of PVB is 25 wt%, the residual ester content is 3 wt%, the molecular weight is 60000 g / mol, the plasticizer is triethylene glycol diisooctanoate, and the Tg is 25℃.

[0055] 2. Preparation steps Polymer support film pretreatment: The polymer support film is subjected to corona discharge treatment to increase its surface tension to 0.045 N / m and remove surface impurities for later use.

[0056] First curing: The pretreated polymer support film is fed to a UV inkjet printer via a roll, and UV-curable ink is deposited onto the film surface in droplet form according to a preset pattern. After printing, a UV lamp with 50% power is used for the first curing, with a curing time of 2 seconds, so that the ink remains viscous but is not fully cross-linked, resulting in the printed polymer support film.

[0057] Lamination and Second Curing: The polymer film and the printed polymer support film are laminated using a laminator, sandwiching the UV-printed image layer between the polymer support film and the polymer film. The lamination temperature is 80℃ and the pressure is 0.3MPa. After lamination, a second curing is performed using a 100% power UV lamp for 3 seconds, allowing the UV-printed image layer to fully cross-link and cure, forming a stable printed composite layer.

[0058] Lamination and Pressing: The outer glass layer, first adhesive layer, printed composite layer, second adhesive layer, and inner glass layer are laminated sequentially, ensuring alignment and neat edges to obtain a laminated body. The laminated body is passed through room temperature pressure rollers to expel trapped air between layers. It is then heated by infrared radiation until the glass surface temperature reaches 100°C, and further pressed by a second pair of rollers to achieve temporary bonding and sealing, resulting in a pre-pressed component. This component is then placed in an autoclave at 135°C and 1150 kN / m². 2 Under these conditions, maintain for 40 minutes to allow each adhesive layer to completely melt and solidify. Then, trim and clean the edges to form the final high-performance decorative laminated glass with UV-printed images.

[0059] Example 2 The difference between this embodiment and Embodiment 1 is that: The addition of scattering particles in the UV-curable ink was omitted, and the amount of UV-curable resin (HDDA) was adjusted to 80.2 wt%.

[0060] Example 3 The difference between this embodiment and Embodiment 1 is that: (1) The polymer film selected is an EVA film with a thickness of 0.127 mm (the melt index of EVA is 10 g / 10 min). (2) The addition of scattering particles in UV-curable ink is omitted, and the amount of UV-curable resin (HDDA) is adjusted to 80.2 wt%.

[0061] Example 4 The difference between this embodiment and Embodiment 1 is that: The polymer film used is an EVA film with a thickness of 0.127 mm (the melt index of EVA is 10 g / 10 min).

[0062] Example 5 The difference between this embodiment and Embodiment 1 is that: (1) The thickness of the outer glass (annealed soda-lime glass) is adjusted to 1.5 mm; (2) The inner glass is chemically strengthened soda-lime glass with a thickness of 0.05 mm (soda-lime glass is placed in potassium nitrate solution for ion exchange treatment, and a compressive stress layer is formed on its surface to obtain chemically strengthened soda-lime glass). Specifically, its surface compressive stress is 350 MPa and the compressive stress layer depth is 12 μm. (3) The thickness of the polymer support film (PVB film) is adjusted to 0.2032 mm; (4) The thickness of the polymer film (TPU film) is adjusted to 0.1016 mm; (5) The addition of scattering particles in UV-curable ink is omitted, and the amount of UV-curable resin (HDDA) is adjusted to 80.2 wt%.

[0063] Example 6 The difference between this embodiment and Embodiment 1 is that: (1) The outer glass is heat-strengthened glass with a thickness of 3mm (the glass is heated to 635℃ and held for 45s, then cooled by blowing air at a medium cooling rate, and the final surface stress is controlled at 24-52MPa by adjusting the pressure of the cooling air grid to obtain heat-strengthened glass). (2) The inner glass is chemically strengthened borosilicate glass with a thickness of 1.2 mm (the borosilicate glass is placed in potassium nitrate solution for ion exchange treatment, and a compressive stress layer is formed on its surface to obtain chemically strengthened borosilicate glass). Specifically, its surface compressive stress is 450 MPa and the compressive stress layer depth is 25 μm. (3) The polymer support membrane is a PET membrane with a thickness of 0.305 mm (the molecular weight of PET is 22000 g / mol, and the PET membrane is subjected to biaxial stretching and heat stabilization treatment. After being exposed at 150℃ for 30 min, the bidirectional shrinkage rate is: 0.5% in the longitudinal direction and 0.3% in the transverse direction). (4) The polymer film is an EVA film with a thickness of 0.152 mm (the melt index of EVA is 10 g / 10 min). (5) The addition of scattering particles in UV-curable ink is omitted, and the amount of UV-curable resin (HDDA) is adjusted to 80.2 wt%.

[0064] Comparative Example 1 The difference between this comparative example and Example 1 is as follows: (1) The inner glass is made of annealed soda-lime glass with a thickness of 2.1 mm (the same as the outer glass). (2) The use of polymer film is omitted; (3) The addition of scattering particles in UV-curable ink is omitted, and the amount of UV-curable resin (HDDA) is adjusted to 80.2 wt%.

[0065] Comparative Example 2 The difference between this comparative example and Example 1 is as follows: (1) The use of polymer film is omitted; (2) The addition of scattering particles in UV-curable ink is omitted, and the amount of UV-curable resin (HDDA) is adjusted to 80.2 wt%.

[0066] Comparative Example 3 The difference between this comparative example and Example 1 is as follows: (1) The polymer film is a 0.127 mm thick PVB film (the PVB film contains PVB and plasticizer; the hydroxyl content of PVB is 25 wt%, the residual ester content is 3 wt%, and the molecular weight is 60000 g / mol; the plasticizer is triethylene glycol diisooctanoate, and the plasticizer content in the PVB film is 30 wt%). (2) The addition of scattering particles in UV-curable ink is omitted, and the amount of UV-curable resin (HDDA) is adjusted to 80.2 wt%.

[0067] The high-performance decorative laminated glasses with ultraviolet-printed images prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to performance tests according to the following standards or methods: (1) Compression shear strength: The test was conducted in accordance with GB / T 7124 (Determination of tensile shear strength of adhesives). The specimen was loaded at a tensile speed of 5 mm / min under the conditions of temperature 23±2℃ and relative humidity 50±5%. The maximum load at which the specimen failed was recorded and the compression shear strength value (MPa) was calculated. (2) Stone impact fracture rate: The test was conducted in accordance with GB / T 2843 (Test Methods for Automotive Safety Glass Part 3: Impact Resistance Test). A ball bearing with a mass of 1 gram was used as the impactor, and the laminated glass specimen was subjected to impact test at an incident angle of 45 degrees. Within the speed range of 75-85 mph, the percentage of impacts in which the specimen broke was recorded as the stone impact fracture rate.

[0068] (3) Transmittance: The transmittance was tested in accordance with GB / T 2410 (Determination of transmittance and haze of transparent plastics). A D65 light source was used to measure the transmittance (%) of the sample in the visible light wavelength range of 380-780nm using an integrating sphere spectrophotometer. (4) Haze: The test shall be conducted in accordance with GB / T 2410 "Determination of transmittance and haze of transparent plastics". Under the same test conditions as transmittance, the scattered light flux passing through the sample shall be measured, and the proportion of scattered light shall be calculated according to the standard method to obtain the haze value (%).

[0069] The performance test results are recorded in Table 1.

[0070] Table 1 Performance Test Results

[0071] As shown in Table 1, the compressive shear strength of Examples 1-6 of the present invention is ≥7MPa, and the stone impact fracture rate is between 40% and 55%, which is far superior to Comparative Examples 1-3 (compressive shear strength <1MPa, stone impact fracture rate >90%). This indicates that the present invention significantly improves the interlayer adhesion and impact resistance of the laminated glass. Furthermore, Examples 2, 3, 5, and 6 have a light transmittance ≥90% and a haze ≤0.52%, maintaining excellent optical transparency; Examples 1 and 4, due to the addition of scattering particles, have a slightly decreased light transmittance (approximately 80%) and an increased haze to over 22%, achieving a pattern-invisible effect in non-illuminated conditions, meeting the functional requirements of specific decorative scenarios. Comparative Example 1 did not use chemically strengthened inner glass and had no polymer film; Comparative Example 2 had no polymer film; and Comparative Example 3 used PVB as the polymer film. Their mechanical properties are all far lower than those of the embodiments of the present invention, demonstrating that the material selection of the polymer film and the chemical strengthening of the inner glass are crucial for achieving high adhesion and impact resistance.

[0072] Specifically, the core mechanism by which the performance of Comparative Example 3, which uses PVB as a polymer film, deteriorates is as follows: PVB relies on added plasticizers to impart flexibility. During the lamination thermal process, the plasticizers tend to migrate to the interface to form a weak boundary layer. At the same time, its glass transition temperature is close to room temperature, which restricts the movement of chain segments and makes it impossible to effectively dissipate impact energy. In addition, the strong polarity of PVB and the weak polarity of the UV-cured ink layer have poor interfacial compatibility, making it difficult to form a strong chemical bond. This ultimately leads to interfacial delamination and stress concentration, resulting in a significantly lower compressive shear strength than the example using TPU / EVA film, which has intrinsic flexibility, low Tg, and excellent interfacial compatibility.

[0073] In summary, the high-performance decorative laminated glass with ultraviolet printed images provided by this invention significantly improves mechanical properties and functional integration while maintaining excellent optical performance, and has good application prospects.

[0074] Finally, it should be noted that the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A high-performance decorative laminated glass with ultraviolet-printed images, characterized in that, The material comprises an outer glass layer, a first adhesive layer, a printed composite layer, a second adhesive layer, and an inner glass layer, which are stacked sequentially. The printed composite layer comprises a polymer support film, a UV-printed image layer, and a polymer film. The UV-printed image layer is formed on the polymer support film by UV-curing ink printing and is sandwiched between the polymer support film and the polymer film. The polymer film is selected from thermoplastic polyurethane film or ethylene-vinyl acetate copolymer film.

2. The high-performance decorative laminated glass with ultraviolet-printed images according to claim 1, characterized in that, The outer glass layer has a thickness of 1.5-3mm, the inner glass layer has a thickness of 0.05-1.2mm, and the thickness ratio of the outer glass layer to the inner glass layer is 1.25-30.

3. The high-performance decorative laminated glass with ultraviolet-printed images according to claim 1, characterized in that, The polymer support membrane is selected from polyvinyl butyral membrane, polyethylene terephthalate membrane, or ethylene-vinyl acetate copolymer membrane.

4. The high-performance decorative laminated glass with ultraviolet-printed images according to claim 1, characterized in that, The viscosity of the UV-curable ink is 1-50 mPa·s.

5. The high-performance decorative laminated glass with ultraviolet-printed images according to claim 1, characterized in that, The thickness ratio of the polymer film to the polymer support film is ≤1 / 2.

6. The high-performance decorative laminated glass with ultraviolet-printed images according to claim 1, characterized in that, The materials of the first adhesive layer and the second adhesive layer are respectively selected from polyvinyl butyral, thermoplastic polyurethane, ethylene-vinyl acetate copolymer or ionomer.

7. A method for preparing high-performance decorative laminated glass with ultraviolet-printed images as described in any one of claims 1 to 6, characterized in that, Includes the following steps: S1. UV-curable ink is printed onto the surface of the polymer support film, and a first curing is performed to obtain the printed polymer support film; S2. Composite the polymer film with the printed polymer support film, so that the UV printed image layer is located between the polymer support film and the polymer film, and perform a second curing to obtain the printed composite layer; S3. The outer glass, the first adhesive layer, the printed composite layer, the second adhesive layer and the inner glass are stacked in that order and pressed to obtain a high-performance decorative laminated glass with an ultraviolet printed image.

8. The method according to claim 7, characterized in that, In S1, the power of the first curing UV lamp is 30-50%, and the curing time is 1-2 seconds.

9. The method according to claim 7, characterized in that, In S2, the temperature of the composite process is 60-80℃ and the pressure is 0.3-0.5MPa; the power of the UV lamp for the second curing is 80-100% and the time is 2-3s.

10. The method according to claim 7, characterized in that, In S3, the pressing temperature is 130-150℃, and the pressure is 1050-1275kN / m. 2 The time is 30-90 minutes.

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