Adhesive for direct hot stamping of glass substrate as well as preparation method and application of adhesive

Abstract

The invention provides an adhesive for direct hot stamping of a glass substrate as well as a preparation method and application of the adhesive, and belongs to the technical field of hot stamping films. The adhesive comprises the following components in parts by mass: 15-30 parts of matrix resin, 5-10 parts of a nano material modified by a silane coupling agent, 10-20 parts of alicyclic epoxy resin, 0.5-2 parts of a light curing agent and 2-5 parts of a microcapsule curing agent, the matrix resin is any one of an epoxy siloxane prepolymer, acrylic acid esterified silane and acrylic acid esterified polyurethane. The electrochemical aluminum foil prepared from the adhesive can be used for directly hot stamping glass products, and hot stamping films on the surfaces of the obtained glass products are high in adhesive force, good in scratch resistance and excellent in alcohol resistance and cold and heat cycle resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of gold stamping film, and particularly relates to a glass substrate direct gold stamping adhesive as well as a preparation method and application thereof. BACKGROUND

[0002] Electroplated aluminum (gold stamping film) is a kind of gold stamping material made by coating and vacuum evaporation of a layer of metal foil on a film substrate, which is generally composed of five layers of different materials, i.e. base film, release layer, imaging layer, aluminum plating layer and adhesive layer. The material of the base film is generally PET, which mainly serves as a support, and the other layers are all attached to the PET base film. The release layer separates the aluminum plating layer from the base film layer, facilitating foil removal during gold stamping. The imaging layer mainly displays the color of the gold stamping film, and after gold stamping, it can also protect the surface of the gold stamping pattern. The role of the aluminum plating layer is to use the optical properties of aluminum, i.e. high reflectivity and strong light reflection, to make the color light reflected by the imaging layer become a colorful light with metallic luster. The adhesive layer serves as an adhesive to connect the gold stamping film and the gold stamping substrate.

[0003] Glass is a typical inorganic non-metallic material with good transparency and chemical stability, and is widely used in life. At present, the surface decoration effect of glass is mainly realized by electroplating, decal, water transfer printing, etching and other means. The above decoration processes all have the disadvantages of environmental pollution, high energy consumption, single decoration effect, etc. Glass itself has the characteristics of transparency and smoothness, and electroplated aluminum can form high-brightness, mirror or textured decorative patterns (such as patterns, characters, LOGO, etc.) through the reflection and refraction effect of metallic luster, which contrasts with the transparent texture of glass and enhances the high-end feeling and delicacy of the product. Typical applications include high-end cosmetic packaging bottles, luxury glassware, artistic decorative glass, etc., which can improve the brand tone and market premium of the product through the gold stamping process. In addition, the gold stamping process has the advantages of green environmental protection, simple operation and low cost, and can realize electroplated aluminum gold stamping decoration on glass substrate, which will significantly promote environmental protection and improve economic benefits compared with traditional decoration methods.

[0004] However, glass has low polarity, low surface energy and strong chemical inertness, and the physical adsorption force with gold stamping foil is weak, so traditional hot melt adhesive cannot form effective bonding, and direct gold stamping may cause foil peeling and edge lifting. The current solution often requires pre-treatment of the glass surface (such as using a primer, plasma cleaning, sandblasting roughening, etc.), which increases the surface roughness and polarity and improves the adhesion of the foil. However, the above pre-treatment operation is complicated and the adhesion is still insufficient, which is not conducive to industrial production. SUMMARY

[0005] To solve the above problems, the present application provides a kind of adhesive and its preparation method which can be used for direct hot stamping on glass substrate. The adhesion of anodized aluminum prepared by the adhesive on the glass surface is high, and the scratch resistance, alcohol resistance and cold-hot cycle resistance are excellent.

[0006] Specifically, to achieve the above-mentioned purposes, the present application adopts the following technical solutions: An adhesive comprises the following components by mass: 15-30 parts of a main resin, 5-10 parts of a silane coupling agent modified nanomaterial, 10-20 parts of an alicyclic epoxy resin, 0.5-2 parts of a photocuring agent, and 2-5 parts of a microcapsule type curing agent; the main resin is any one of an epoxy siloxane prepolymer, an acrylated silane, and an acrylated polyurethane.

[0007] In a preferred embodiment, the epoxy siloxane prepolymer is a product obtained by hydrolysis and condensation reaction of an epoxy siloxane monomer (3-glycidyloxypropyl triethoxysilane or γ-(2,3-epoxypropoxy)propyl trimethoxysilane), and the epoxy value of the product is 0.4-0.5 eq / 100 g; or the acrylated silane is at least one of acryloyloxypropyl trimethoxysilane and γ-methacryloyloxypropyl trimethoxysilane; or the acrylated polyurethane is at least one of an aliphatic polyurethane acrylate and an aromatic polyurethane acrylate.

[0008] In a preferred embodiment, the nanomaterial is at least one of titanium dioxide nanowire, silicon dioxide nanotube, boron nitride nanotube, carbon nanotube, and zinc oxide nanorod.

[0009] In a preferred embodiment, the silane coupling agent is γ-(2,3-epoxypropoxy)propyl trimethoxysilane or / and acryloyloxypropyl trimethoxysilane.

[0010] In a preferred embodiment, the photocuring agent is a triarylsulfonium salt compound or a free radical photocuring agent.

[0011] In a preferred embodiment, the main component of the microcapsule type curing agent is a eutectic mixture of dicyandiamide and urea or is dicumyl peroxide.

[0012] The present application also provides a preparation method of the adhesive, comprising the following steps: S1, ultrasonic treatment of the nanomaterial in acid solution; the treated nanomaterial is reacted with an alcohol solution of the silane coupling agent under the conditions of pH=4-5 and temperature of 55-65°C, and after the reaction is completed, centrifugation, washing, and drying are performed to obtain the silane coupling agent modified nanomaterial; S2, dissolving the main resin, the alicyclic epoxy resin in an organic solvent, adding the silane coupling agent modified nanomaterial, dispersing to a particle size D of the dispersion 50 <150nm, and then adding the microcapsule curing agent, the photocuring agent and the leveling agent, uniformly mixing and vacuum degassing to obtain the adhesive.

[0013] In a preferred scheme, the silane coupling agent modified nanomaterial in step S2 is added three times with an interval of 5 min each time, and stirring is performed at a speed of 1200 rpm for 15 min after each addition; and then the obtained mixture is grinded by a three-roll grinder to a particle size D 50 <150nm.

[0014] The application further provides an electrochemical aluminum foil comprising the adhesive layer prepared from the adhesive.

[0015] The preparation method of the electrochemical aluminum foil comprises the following steps: coating the adhesive on a metal layer by a microgravure coating method, performing hot air drying at a gradient temperature of 60-80 DEG C, then pre-curing under the protection of inert gas by using ultraviolet light with an irradiation dose of 300-400 mJ / cm 2 , and then winding and aging to obtain the adhesive layer.

[0016] The application further provides a method for directly stamping the electrochemical aluminum foil on a glass product, and the stamping conditions are as follows: stamping for 0.8-1.2 seconds under the conditions of 150-170 DEG C and 0.4-0.6 MPa; and after the stamping is completed, placing the glass product with the stamping film in a heat treatment at 75-85 DEG C for 10-15 minutes.

[0017] Compared with the prior art, the technical scheme of the application has the following beneficial effects: (1) In the application, the one-dimensional nanomaterial is modified by using a silane coupling agent, so that the nanomaterial is staggered into a network in the adhesive layer, a reinforcing skeleton penetrating through the adhesive layer is constructed, and the wear resistance of the stamping film is improved.

[0018] (2) In the application, the primary network is formed by pre-curing under ultraviolet light, and then the microcapsule curing agent is heat-cured to realize deep crosslinking, and under the light-heat dual curing mechanism, the adhesion between the stamping film and the surface of the glass is significantly improved.

[0019] (3) The epoxy-silicone prepolymer is used as the main resin in the present application, and the epoxy group is opened at the hot stamping temperature to form Si-O-C bonds, thereby providing instant and strong initial adhesion, which is much stronger than the adhesion by physical adsorption; then in the thermal curing stage, the Si-O-C bonds react with the Si-OH bonds on the surface of the glass to form a more stable and denser Si-O-Si network structure, thereby achieving more durable and more aging-resistant high adhesion.

[0020] (4) The electrochemical aluminum foil prepared by the adhesive provided by the present application is used for direct hot stamping of glass products, and the gilding film is wiped 500 times with 99% alcohol without any abnormality, the adhesion between the gilding film and the surface of the glass reaches the 5B level, and the pencil hardness is greater than or equal to 4H after 100 times of scraping. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The structure diagram of the electrochemical aluminum foil prepared by the present application.

[0022] In the figure: 1, base film; 2, release layer; 3, imaging layer; 4, metal layer; 5, adhesive layer. DETAILED DESCRIPTION

[0023] The following content combines the embodiments to clearly and completely describe the technical solutions of the present application, so that those skilled in the art can fully understand the present application. Obviously, the described embodiments are only a part of the preferred embodiments of the present application, not all embodiments. Any equivalent transformation or replacement of the following embodiments made by those skilled in the art without creative labor is within the protection scope of the present application.

[0024] Unless otherwise specified, all parts in the present application are mass parts. The methods not described in detail in the specific embodiments of the present application can be realized by conventional methods well known to those skilled in the art.

[0025] The specific embodiments of the present application provide an adhesive consisting of the following mass parts of components: 15-30 parts of main resin, 5-10 parts of silane coupling agent modified nanomaterial, 10-20 parts of alicyclic epoxy resin, 0.5-2 parts of photocuring agent, and 2-5 parts of microcapsule type curing agent; the main resin is any one of epoxy-silicone prepolymer, acrylated silane, and acrylated polyurethane.

[0026] As an example, the parts of the main resin are 15 parts, 16 parts, 17 parts, 18 parts, 20 parts, 24 parts, 25 parts, 26 parts, 28 parts, or 30 parts, without being limited thereto.

[0027] As an example, the parts of the silane coupling agent modified nanomaterial are 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, without being limited thereto.

[0028] By way of example, the cycloaliphatic epoxy resin is present in an amount of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts, without limitation.

[0029] By way of example, the photocuring agent is present in an amount of 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 1.9 parts, or 2 parts, without limitation.

[0030] By way of example, the microcapsule curing agent is present in an amount of 2 parts, 2.2 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, without limitation.

[0031] In some embodiments, the method for preparing the epoxy-silicone prepolymer comprises the following steps: mixing epoxy-silicone monomer, deionized water, ethanol (solvent) in a mass ratio of 1:0.5:9, stirring at 60°C for 4-6 hours (e.g., 4h, 5h, or 6h) at pH = 4-5 (e.g., pH is 4 or 4.5 or 5, acetic acid is used to adjust pH), and then removing the solvent, water and by-products by reduced pressure distillation (e.g., rotary evaporation) to obtain an epoxy-silicone prepolymer with an epoxy value of 0.4-0.5 eq / 100g (e.g., 0.4 eq / 100g, 0.45 eq / 100g, or 0.5 eq / 100g). By way of example, the epoxy-silicone monomer is a combination of one or both of 3-glycidyloxypropyl triethoxysilane (KBE-403, Shin-Etsu, Japan) and γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560, or GLYMO from Sigma).

[0032] In some embodiments, the acrylated silane is at least one of acryloxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. For example, SCA-100 (Shin-Etsu, Japan) and A-174 (Dow Corning, USA).

[0033] In some embodiments, the acrylated polyurethane is at least one of aliphatic polyurethane acrylate and aromatic polyurethane acrylate. For example, CN966 (Sartomer) and CN2920 (Sartomer).

[0034] In some embodiments, the silane coupling agent is at least one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane and acryloxypropyltrimethoxysilane.

[0035] In some embodiments, the nanomaterial is at least one of titanium dioxide nanowires, silicon dioxide nanotubes, boron nitride nanotubes, carbon nanotubes, and zinc oxide nanorods. For example, the nanomaterial is titanium dioxide nanowires with a diameter of 20-50 nm and an aspect ratio > 20. By way of example, the diameter of the titanium dioxide nanowires is 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm, without limitation; and the aspect ratio is 22, 25, 26, or 28, without limitation.

[0036] In some embodiments, the alicyclic epoxy resin is GER-170 from Showa Denko or GLYMO (chemical name: γ-(2,3-epoxypropoxy)propyltrimethoxysilane) from Sigma.

[0037] In some embodiments, the photocuring agent is UVI-6992 (triphenylsulfonium hexafluorophosphate salt) from DOW, UVI-6976 (triphenylsulfonium hexafluoroantimonate salt) from DOW, or Irgacure 1173 (2-hydroxy-2-methylphenylpropanone) from BASF.

[0038] In some embodiments, the method for preparing the microcapsule curing agent comprises the following steps: T1-1, mixing dicyandiamide and urea at a mass ratio of 3:1 to obtain a first mixture. The first mixture is added to a 2 wt% polyvinyl alcohol (PVA-217) aqueous solution at an amount of 0.05 g per ml to obtain an aqueous phase. Methyl methacrylate and butyl acrylate are mixed at a mass ratio of 7:3 to obtain a second mixture. 2 wt% of an initiator (e.g., azobisisobutyronitrile) based on the total mass of the second mixture is added to the second mixture and mixed uniformly to obtain an oil phase.

[0039] T1-2, mixing the aqueous phase and the oil phase, stirring at 15000 rpm at 60°C for 10 minutes to form an emulsion. The emulsion is warmed to 75°C for polymerization for 4 hours. After the reaction is completed, it is cooled, filtered, and the solid is dried at 40°C to obtain a white powder, which is the microcapsule curing agent. The particle size of the microcapsule is 1-3 μm as detected by a laser particle size analyzer. The wall thickness of the microcapsule is 0.2±0.05 μm as characterized by SEM.

[0040] In some other embodiments, the method for preparing the microcapsule curing agent comprises the following steps: T2-1, synthesis of the prepolymer: 20 parts of urea, 12 parts of 37% formaldehyde aqueous solution, and 50 parts of deionized water are added to a three-necked flask with a stirrer and a condenser. The pH value of the solution is adjusted to 8.0-8.5 with triethanolamine. Stirring is performed at 70°C for 1 hour to form a transparent water-soluble urea-formaldehyde resin prepolymer; and the solution is cooled to room temperature for standby use.

[0041] T2-2, oil phase preparation and emulsification: DCP (dicumyl peroxide) was dissolved in toluene to form a uniform oil phase. 50 parts of deionized water and 0.5 parts of emulsifier (sodium dodecyl benzene sulfonate, SDBS) were added to another reaction container, stirred uniformly to obtain an aqueous phase. Under high-speed (5000 rpm) shearing, the oil phase was slowly added to the aqueous phase, and shearing was continued for 10 minutes to form a stable O / W (oil-in-water) emulsion, and the emulsion droplet size should be controlled at 2-5 μm.

[0042] T2-3, polymerization and curing of microcapsules: the water-soluble urea-formaldehyde resin prepolymer prepared in step T2-1 was slowly added to the emulsion obtained in step T2-2, and slowly stirred at a speed of 300-500 rpm with a mechanical stirrer for 30 min. Then the pH value of the system was slowly adjusted to 3.0-3.5 with a citric acid solution, and the reaction was slowly stirred at 55°C for 2 hours.

[0043] T2-4, post-treatment and drying: after the reaction in step T2-3 was completed, it was cooled to room temperature, filtered, and the microcapsule solid was separated, washed with deionized water and ethanol alternately for three times each, and the filter cake was dried in a vacuum oven at 40°C for 12 hours to obtain a white DCP microcapsule powder.

[0044] As an example, the solution pH value in step T2-1 was adjusted to 8.0, 8.1, 8.2, 8.3, 8.4 or 8.5 with triethanolamine, not limited thereto.

[0045] As an example, the emulsion droplet size in step T2-2 was controlled to 2 μm, 3 μm, 4 μm or 5 μm.

[0046] As an example, the stirring speed in step T2-3 was 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm.

[0047] As an example, the pH value of the system in step T2-3 was slowly adjusted to 3.0, 3.1, 3.2, 3.3, 3.4 or 3.5 with a citric acid solution, not limited thereto.

[0048] The specific embodiment of the present application further provides a preparation method of an adhesive, comprising the following steps: S1, the nanomaterial is placed in 10wt% HNO3 aqueous solution, and is treated by ultrasonic wave at 40 kHz and 100 W for 30 min. γ-(2, 3-epoxypropoxy) propyl trimethoxysilane is mixed with ethanol at a mass ratio of 1:9 to obtain an alcohol solution of silane coupling agent. The nanomaterial after ultrasonic treatment is reacted with the alcohol solution of silane coupling agent under the conditions of pH = 4-5 (adjusted by acetic acid) and temperature of 55-65 ℃ for 4-6 hours. After the reaction is completed, the mixture is centrifuged at a speed of 8000 rpm, the solid is washed with deionized water until the conductivity is <20 μS / cm, and then vacuum dried at 80 ℃ for 6 hours to obtain the nanomaterial modified by silane coupling agent. The nanomaterial modified by silane coupling agent is detected by X-ray photoelectron spectroscopy (XPS), and the grafting density is ≥3.8 epoxy groups / nm 2 The nanomaterial modified by silane coupling agent is placed in ethanol and ultrasonicated (ultrasonic power is 100 W, frequency is 40 kHz) for 30 min without precipitation.

[0049] S2, the main resin and alicyclic epoxy resin are dissolved in an organic solvent, and a planetary mixer is used to stir at a revolution speed of 300-600 rpm and a rotation speed of 0-200 rpm for 10 min, and the temperature of the mixed system is controlled to be <40 ℃ during the stirring process to obtain a uniformly mixed mixture A1. The nanomaterial modified by silane coupling agent is added to the mixture A1 in three times, and the time interval of each addition is 5 min, and the mixture A1 is stirred at a speed of 1200 rpm for 15 min after each addition, and a uniformly mixed mixture A2 is obtained. The mixture A2 is ground by a three-roll grinder, and the dispersion is ground in cycles for three times until the particle size D 50 <150 nm. The first roll gap of the three-roll grinder is 50 μm, the second roll gap is 20 μm, and the third roll gap is 5 μm; the roller temperature is 30-40 ℃ (water cooling cycle). The microcapsule curing agent is added to the ground mixture A2 under the stirring speed of <800 rpm (to prevent the microcapsule from being broken), and then the photocuring agent and the leveling agent are added, and the mixture is stirred at a speed of 800 rpm for 5 min. The dispersion obtained is degassed under a vacuum degree of -0.095 MPa for 30 min to obtain the adhesive. The viscosity of the adhesive is 4000-5000 cps.

[0050] For example, the pH condition for the reaction of the nanomaterial after ultrasonic treatment in step S1 with the alcohol solution of silane coupling agent is 4, 4.5 or 5, and is not limited thereto.

[0051] For example, the temperature for the reaction of the nanomaterial after ultrasonic treatment in step S1 with the alcohol solution of silane coupling agent is 55 ℃, 58 ℃, 60 ℃, 62 ℃ or 65 ℃, and is not limited thereto.

[0052] As an example, the time for the reaction of the nanomaterial after the ultrasonic treatment in step S1 with the alcohol solution of the silane coupling agent is 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, without being limited thereto.

[0053] As an example, the revolution speed of the planetary mixer in step S2 is 300 rpm, 320 rpm, 350 rpm, 360 rpm, 380 rpm, 400 rpm, 430 rpm, 460 rpm, 480 rpm, 500 rpm, 550 rpm, or 600 rpm, without being limited thereto.

[0054] As an example, the revolution speed of the planetary mixer in step S2 is 300 rpm, 320 rpm, 350 rpm, 360 rpm, 380 rpm, 400 rpm, 430 rpm, 460 rpm, 480 rpm, 500 rpm, 550 rpm, or 600 rpm, without being limited thereto.

[0055] In a preferred embodiment, the revolution speed of the planetary mixer in step S2 is 500 rpm, and the rotation speed is 100 rpm.

[0056] As an example, the roller temperature in step S2 is 30℃, 32℃, 35℃, 36℃, 38℃, or 40℃, without being limited thereto.

[0057] The detailed embodiment of the present application further provides an electrochemical aluminum foil, as shown in the drawing, which comprises a base film 1, a release layer 2, an imaging layer 3, a metal layer 4, and an adhesive layer 5 which are sequentially stacked. Figure 1

[0058] As an example, the material of the base film 1 is polyethylene terephthalate (PET).

[0059] In a preferred embodiment, the material of the release layer 2 is any one of silicone resin, wax, or acrylic resin. As an example, the material of the release layer is X-22-161B of Shin-Etsu Chemical.

[0060] In a preferred embodiment, the material of the imaging layer 3 is any one of thermosetting acrylic resin, saturated copolyester resin, or thermoplastic acrylic resin. For example, the material of the imaging layer is SETALUX 2127 XX-60, SETALUX 57-1277, SETALUX 27-1592, VIACRYL FC 1925 BA-75, or VIACRYL SC121 / 60X of ALLNEX. ® 2127 XX-60, SETALUX ® 57-1277, SETALUX ® 27-1592, SETALUX ® FC 1925 BA-75, VIACRYL ® SC121 / 60X.

[0061] ​As an example, the material of the metal layer 4 is aluminum or tin.

[0062] The preparation method of the adhesive layer 5 comprises the following steps: P1, the adhesive in Example 1 is coated on the metal layer by micro-gravure coating method using a precision coater with a mesh size of 180 lines / cm, the coating speed is 12-18 m / min, and the coating amount is 4.0-5.0 g / m 2 After coating, the wet film is obtained by peeling off, and the thickness of the wet film is 23-27 μm (monitored by an online beta-ray thickness gauge).

[0063] P2, the wet film is placed in a hot air floatation drying box, first dried at 60°C hot air for 30 s, the wind speed is 8 m / s; then dried at 70°C hot air for 15 s, the wind speed is 8 m / s; and then dried at 80°C hot air for 15 s, the wind speed is 5 m / s.

[0064] P3, after drying, the dried adhesive layer is irradiated under nitrogen protection (oxygen concentration <200 ppm) with a 120 W / cm mercury lamp (365 nm) at an irradiation dose of 300-400 mJ / cm 2 (monitored by UVPF-36 cumulative light meter) for ultraviolet pre-curing (FTIR monitors 915 cm -1 peak, the conversion rate of epoxy group is 30%-40%), and then wound, and the winding diameter is ≤600 mm to prevent the microcapsule curing agent from being crushed.

[0065] As an example, the coating speed in step P1 is 12 m / min, 13 m / min, 14 m / min, 15 m / min, 16 m / min, 17 m / min, or 18 m / min, without being limited thereto.

[0066] As an example, the coating amount of the adhesive in step P1 is 4.0 g / m 2 , 4.2 g / m 2 , 4.5 g / m 2 , 4.8 g / m 2 or 5.0 g / m 2 , without being limited thereto.

[0067] As an example, the thickness of the wet film in step P1 is 23 μm, 24 μm, 25 μm, 26 μm, or 27 μm, without being limited thereto.

[0068] As an example, the irradiation dose in step P3 is 300 mJ / cm 2 , 305 mJ / cm 2 , 310 mJ / cm 2 , 315 mJ / cm 2 , 320 mJ / cm2 325 mJ / cm 2 330 mJ / cm 2 350 mJ / cm 2 360 mJ / cm 2 380 mJ / cm 2 or 400 mJ / cm 2 , without being limited thereto.

[0069] The detailed description of the application further provides a method for preparing a glass product with a gilded film, comprising the following steps: directly gilding an aluminum foil onto a common soda-lime glass product under the following gilding conditions: gilding for 0.8-1.2 seconds at 150-170°C (measured surface temperature of the glue layer), 0.4-0.6 MPa (pneumatic pressure), and then air cooling (air speed: 10 m / s) to 60°C for peeling. After gilding, the glass product with the gilded film is heat treated in an oven at 75-85°C for 10-15 minutes to make the microcapsule curing agent break and release the curing agent (dicyandiamide release amount > 95% by HPLC detection), and to perform deep cross-linking to strengthen the cohesive energy of the adhesive layer. The heating rate for heat treatment at 80°C is 2°C / min to prevent bubbles from being generated due to rapid heating.

[0070] As an example, the gilding temperature is 150°C, 155°C, 160°C, 165°C, or 170°C, without being limited thereto.

[0071] As an example, the gilding pressure is 0.4 MPa, 0.5 MPa, or 0.6 MPa, without being limited thereto.

[0072] As an example, the gilding time is 0.8 s, 0.9 s, 1.0 s, or 1.2 s, without being limited thereto.

[0073] As an example, the heat treatment temperature is 75°C, 77°C, 78°C, 80°C, 82°C, or 85°C, without being limited thereto.

[0074] As an example, the heat treatment time is 10 min, 11 min, 12 min, 14 min, or 15 min, without being limited thereto.

[0075] Example 1 An adhesive, the composition of which is as follows: 25 parts of epoxy siloxane prepolymer (monomer GLYMO, epoxy value of the prepolymer 0.45 eq / 100g), 15 parts of alicyclic epoxy resin (CER-170, Japan Chemical), 8 parts of γ-(2,3-epoxypropoxy) propyl trimethoxysilane modified TiO2 nanowire (diameter of TiO2 nanowire 30 nm, aspect ratio 25, rutile type, Xuancheng Jingrui), 3 parts of microcapsule curing agent, 1.5 parts of cationic photocuring agent (UVI-6992, DOW), 0.3 parts of leveling agent (BYK-371), 35 parts of propylene glycol methyl ether acetate (organic solvent).

[0076] The preparation method of the adhesive comprises the following steps: S1, the TiO2 nanowire is placed in a 10wt% HNO3 aqueous solution and treated with ultrasonic waves at 40 kHz and 100 W for 30 min. γ-(2,3-epoxypropoxy) propyl trimethoxysilane is mixed with ethanol at a mass ratio of 1:9 to obtain an alcohol solution of silane coupling agent. The ultrasonic-treated TiO2 nanowire is reacted with the alcohol solution of silane coupling agent at pH=4.5 (adjusted with acetic acid) and a temperature of 60℃ for 4 hours. After the reaction is completed, the mixture is centrifuged at 8000 rpm, the solid is washed with deionized water until the conductivity is <20 μS / cm, and then vacuum dried at 80℃ for 6 hours to obtain a silane coupling agent-modified nanomaterial. The silane coupling agent-modified nanomaterial is detected by X-ray photoelectron spectroscopy (XPS) and the grafting density is 4.5 epoxy groups / nm 2 The silane coupling agent-modified nanomaterial is ultrasonically treated (ultrasonic power 60 W, frequency 20 kHz) in ethanol for 30 min without precipitation.

[0077] S2, the epoxy siloxane prepolymer and the alicyclic epoxy resin are dissolved in the organic solvent, and a planetary mixer is used to stir at a revolution speed of 500 rpm and a rotation speed of 100 rpm for 10 min. The temperature of the mixed system is controlled to be <40℃ during the stirring process, and a uniformly mixed mixture A1 is obtained. The silane coupling agent-modified nanomaterial is added to the mixture A1 in three times, and the time interval between each addition is 5 min. After each addition, the mixture is stirred at a speed of 1200 rpm for 15 min, and a uniformly mixed mixture A2 is obtained. The mixture A2 is ground by a three-roll grinder, and the dispersion is ground in cycles for three times until the particle size D 50<150 nm. The first nip of the three-roll mill was 50 μm, the second nip was 20 μm, and the third nip was 5 μm; the roller temperature was 35°C (water cooling cycle). After the mixture A2 was ground, the microcapsule curing agent was added to the mixture under stirring at <800 rpm (to prevent the microcapsules from breaking), and then the photocuring agent and the leveling agent were added. The mixture was stirred at 800 rpm for 5 minutes. The dispersion was degassed at a vacuum degree of -0.095 MPa for 30 minutes, and the adhesive was obtained. The viscosity of the adhesive was 4500 cps.

[0078] Example 2 An electrochemical aluminum foil (reference Figure 1 ) was prepared by sequentially laminating a base film 1, a release layer 2, an imaging layer 3, a metal layer 4, and an adhesive layer 5. The base film 1 was made of polyethylene terephthalate (PET). The release layer 2 was made of silicone resin (Shin-Etsu Chemical X-22-161B). The imaging layer 3 was made of thermoplastic acrylic resin (SETALUX ® 2127 XX-60). The metal layer 4 was made of aluminum. The adhesive layer 5 was prepared by using the adhesive of Example 1. The electrochemical aluminum foil was prepared by using conventional techniques in the art.

[0079] The method for preparing the adhesive layer included the following steps: P1, the adhesive of Example 1 was coated on the metal layer by using a precision coater with a mesh specification of 180 lines / cm by microgravure coating, the coating speed was 15 m / min, and the coating amount was 4.5 g / m 2 After the coating was completed, the wet film was peeled off, and the thickness of the wet film was 25 μm (monitored by an online beta-ray thickness gauge).

[0080] P2, the wet film was placed in a hot air floatation drying box, and first dried at 60°C under hot air for 30 s at a wind speed of 8 m / s; then dried at 70°C under hot air for 15 s at a wind speed of 8 m / s; and then dried at 80°C under hot air for 15 s at a wind speed of 5 m / s.

[0081] P3, after the drying was completed, the dried adhesive layer was irradiated by a mercury lamp (365 nm) at 120 W / cm under nitrogen protection (oxygen concentration was controlled to be <200 ppm) at an irradiation dose (UVPF-36 cumulative light quantity meter monitoring) of 300 mJ / cm 2 The UV pre-curing was monitored by FTIR at a peak of 915 cm -1 , and the conversion rate of the epoxy group was measured to be 35%. Then the adhesive layer was wound, and aged at 40°C for 48 h; the winding diameter was ≤600 mm to prevent the microcapsule curing agent from being crushed.

[0082] Example 3 A method for preparing a glass product with a gilded film, comprising the following steps: directly gilding the electrochemical aluminum foil in Example 2 to a common soda-lime glass product under the gilding conditions of 160°C (measured temperature of the surface of the glue layer), 0.5 MPa (pneumatic pressure) for 1.0 seconds, and then air cooling (air speed of 10 m / s) to 60°C for peeling. After gilding is completed, the glass product with a gilded film is heat treated in an 80°C oven for 10 minutes to make the microcapsule curing agent break and release the curing agent (dicyandiamide release amount > 95% by HPLC detection), and to perform deep cross-linking to strengthen the cohesive energy of the adhesive layer. The heating rate for heat treatment at 80°C is 2°C / min to prevent bubbles from being generated due to rapid heating.

[0083] Example 4 An adhesive, the constituent components of which are as follows: 20 parts of an epoxy siloxane prepolymer (monomer GLYMO, epoxy value of the prepolymer 0.4 eq / 100 g), 18 parts of a cycloaliphatic epoxy resin (UVR-6105, Dow Chemical), 6 parts of γ- (2, 3-epoxypropoxy) propyl trimethoxysilane modified TiO2 nanowires (diameter of the TiO2 nanowires 20 nm, aspect ratio 28, rutile type, Xuancheng Jingrui), 4 parts of a microcapsule curing agent, 1 part of a cationic photocuring agent (UVI-6976, Dow Chemical), 0.3 parts of a leveling agent (BYK-371), and 40 parts of propylene glycol methyl ether acetate (organic solvent).

[0084] The method for preparing the adhesive comprises the following steps: S1, the TiO2 nanowires are placed in a 10wt% HNO3 aqueous solution and treated with ultrasonic waves at 40 kHz and 100 W for 30 min. The γ- (2, 3-epoxypropoxy) propyl trimethoxysilane is uniformly mixed with ethanol at a mass ratio of 1:9 to obtain an alcohol solution of the silane coupling agent. The ultrasonic-treated TiO2 nanowires are reacted with the alcohol solution of the silane coupling agent at pH = 4 (adjusted with acetic acid) and a temperature of 65°C for 5 hours. After the reaction is completed, the mixture is centrifuged at a speed of 8000 rpm, the solid is washed with deionized water until the conductivity is < 20 μS / cm, and then vacuum dried at 80°C for 6 hours to obtain the nanomaterial modified with the silane coupling agent. The nanomaterial modified with the silane coupling agent is detected by X-ray photoelectron spectroscopy (XPS) and the grafting density is 4.0 epoxy groups / nm 2 The nanomaterial modified with the silane coupling agent is ultrasonically treated (ultrasonic power 60 W, frequency 20 kHz) in ethanol for 30 min without precipitation.

[0085] S2, the epoxy siloxane prepolymer, alicyclic epoxy resin is dissolved in organic solvent, using the planetary mixer with 500 rpm revolution speed and 100 rpm rotation speed stirring 10 min, the temperature of the mixed system is controlled <40℃ during the stirring process, the mixture A1 is obtained. The silane coupling agent modified nanomaterial is added into the mixture A1 for three times, the time interval of each addition is 5 minutes, and the stirring speed is 1200 rpm for 15 min after each addition, the mixture A2 is obtained after mixing uniformly. The mixture A2 is grinded by three-roll mill, the dispersion particle size D 50 <150 nm. The first roll gap of the three-roll mill is 50 μm, the second roll gap is 20 μm, and the third roll gap is 5 μm; the roll temperature is 30℃ (water cooling circulation). The microcapsule curing agent is added into the grinded mixture A2 under the stirring speed of <800 rpm (to prevent the microcapsule from breaking), then the light curing agent and the leveling agent are added, and the stirring speed is 800 rpm for 5 min. The dispersion liquid is degassed under the vacuum degree of -0.095 MPa for 30 min, and the adhesive is obtained. The viscosity of the adhesive is 4000 cps after detection.

[0086] Example 5 Reference Figure 1 The present embodiment provides an electrochemical aluminum foil, which has the same structure as the electrochemical aluminum foil in Example 2, and the difference is that the adhesive layer is prepared by using the adhesive of Example 4, and the coating amount in step P1 is 5 g / m 2 , and the thickness of the wet film is 27 μm.

[0087] Example 6 A method for preparing a glass product with a gilded film, comprising the following steps: directly stamping the electrochemical aluminum foil in Example 5 onto a common soda-lime glass product, and the stamping conditions are as follows: stamping for 1.2 seconds under 170℃ (the actual measured temperature of the adhesive layer surface) and 0.4 MPa (pneumatic pressure), and then air cooling (the air speed is 10 m / s) to 60℃ for peeling. After stamping, the glass product with the gilded film is heat treated in an oven at 85℃ for 13 minutes, so that the microcapsule curing agent is broken to release the curing agent (the release amount of dicyandiamide is >95% by HPLC detection), and the cohesive energy of the adhesive layer is crosslinked and strengthened. The heating rate of the heat treatment at 80℃ is 2℃ / min to prevent bubbles from being generated due to rapid heating.

[0088] Comparative Example 1 An adhesive, which comprises the following components: 40 parts of a thermoplastic acrylic resin (ZHL-1063, Di'aisen), 10 parts of methyl methacrylate, 5 parts of silica matting powder, and 45 parts of ethyl acetate (organic solvent).

[0089] The preparation method of the adhesive comprises the following steps: dissolving the thermoplastic acrylic resin in ethyl acetate, then sequentially adding methyl methacrylate and silica matting powder, uniformly mixing by mechanical stirring, defoaming, and filtering to obtain the adhesive. The adhesive system does not introduce any component (such as a silane coupling agent) that can form a chemical bond with the surface of the glass.

[0090] Comparative Example 2 The structure of the anodized aluminum foil provided in the present comparative example is the same as that in Example 2, except that the adhesive layer is prepared from the adhesive of Comparative Example 1, and the preparation method of the adhesive layer does not include step P3 in Example 2.

[0091] Comparative Example 3 A method for preparing a glass product with a gold foil, comprising the following steps: directly stamping the anodized aluminum foil in Comparative Example 2 onto a common soda-lime glass product, and the stamping conditions are substantially the same as those in Example 3, except that the stamping is ended after air cooling to 60°C and peeling, and a glass product with a gold foil is obtained.

[0092] Comparative Example 4 An adhesive, comprising the following components: 25 parts of an epoxy siloxane prepolymer (monomer GLYMO, epoxy value of the prepolymer is 0.45 eq / 100 g), 15 parts of a cycloaliphatic epoxy resin (CER-170, Japan Chemicals), 3 parts of a microcapsule curing agent, 1.5 parts of a cationic photocuring agent (UVI-6992, DOW), 0.3 parts of a leveling agent (BYK-371), and 35 parts of propylene glycol methyl ether acetate (organic solvent). Compared with Example 1, the adhesive of the present comparative example does not add TiO2 nanowires modified by a silane coupling agent.

[0093] Comparative Example 5 The structure of the anodized aluminum foil provided in the present comparative example is the same as that in Example 2, except that the adhesive layer is prepared from the adhesive of Comparative Example 4. The preparation method of the adhesive layer is the same as that in Example 2, except that the components of the adhesive are different.

[0094] Comparative Example 6 A method for preparing a glass product with a gold foil, comprising the following steps: directly stamping the anodized aluminum foil in Comparative Example 5 onto a common soda-lime glass product, and the stamping conditions are the same as those in Example 3.

[0095] Comparative Example 7 An adhesive, the composition of which is as follows: 25 parts of epoxy siloxane prepolymer (monomer GLYMO, epoxy value of the prepolymer 0.45 eq / 100g), 15 parts of alicyclic epoxy resin (CER-170, Japan Chemical), 8 parts of γ-(2,3-epoxypropoxy) propyl trimethoxysilane modified TiO2 nanowires (diameter of the TiO2 nanowires 30 nm, aspect ratio 25, rutile type, Xuancheng Jingrui), 3 parts of dicyandiamide curing agent (DICY-P, Foshan Pluronic), 1.5 parts of cationic photocuring agent (UVI-6992, DOW), 0.3 parts of leveling agent (BYK-371), 35 parts of propylene glycol methyl ether acetate (organic solvent). That is, compared with Example 1, the adhesive provided by the present comparative example directly uses a dicyandiamide curing agent in the composition of the adhesive, instead of preparing a microcapsule curing agent.

[0096] Comparative Example 8 The structure of the anodized aluminum foil provided by the present comparative example is the same as that in Example 2, except that the adhesive layer is prepared from the adhesive of Comparative Example 7. The preparation method of the adhesive layer is the same as that in Example 2, except that the composition of the adhesive is different. Since the dicyandiamide curing agent is directly added, the adhesive is partially crosslinked during the process of winding and curing, resulting in a decrease in activity during subsequent hot stamping.

[0097] Comparative Example 9 A method for preparing a glass product with a gold stamping film, comprising the following steps: directly hot stamping the anodized aluminum foil in Comparative Example 8 onto a common soda-lime glass product, the hot stamping conditions being substantially the same as in Example 3, except that the hot stamping is ended after air cooling to 60°C for peeling (since the dicyandiamide curing agent has been pre-added, there is no need for heat treatment to break the microcapsules), thereby obtaining a glass product with a gold stamping film.

[0098] Comparative Example 10 An adhesive, the composition of which is as follows: 40 parts of bisphenol A epoxy resin (CYD-128, Zhengzhou Hongxun), 8 parts of γ-(2,3-epoxypropoxy) propyl trimethoxysilane modified TiO2 nanowires (diameter of the TiO2 nanowires 30 nm, aspect ratio 25, rutile type, Xuancheng Jingrui), 3 parts of microcapsule curing agent, 1.5 parts of cationic photocuring agent (UVI-6992, DOW), 0.3 parts of leveling agent (BYK-371), 35 parts of propylene glycol methyl ether acetate (organic solvent). That is, the adhesive of the present comparative example is different from Example 1 in that 40 parts of bisphenol A epoxy resin is used instead of 25 parts of epoxy siloxane prepolymer and 15 parts of alicyclic epoxy resin in Example 1.

[0099] Comparative Example 11 The structure of the anodized aluminum foil provided by the present comparative example is the same as that in Example 2, except that the adhesive layer is prepared from the adhesive of Comparative Example 10. The preparation method of the adhesive layer is the same as that in Example 2, except that the composition of the adhesive is different.

[0100] Comparative Example 12 A method for preparing a glass product with a gilded film, comprising the following steps: directly gilding the anodized aluminum foil in Comparative Example 11 onto a common soda-lime glass product, and the gilding conditions are the same as those in Example 3.

[0101] Product performance test The performance of the gilded film of the glass product with a gilded film prepared in Examples 3, 6 and Comparative Examples 3, 6, 9, 12 (the common soda-lime glass product used in the above examples and comparative examples is the same product) is tested, and the test results are shown in Table 1.

[0102] 1. Adhesion test: The crosshatch method in ASTM D3359 is used, and the adhesion level is divided into 0B-5B levels.

[0103] 2. Alcohol resistance test: A 500g weight is wrapped with a cotton cloth soaked with alcohol (99% ethanol), and is vertically placed on the surface of the gilded film. No pressure is applied in the vertical direction, and the weight is slid back and forth (reciprocal for one time) in the horizontal direction. The sliding speed is 20-30 times / min (for example, 30 times / min), and the stroke is 100mm. The number of times of obvious wear or peeling of the pattern is recorded.

[0104] 3. Scratch resistance test: A 500g weight is wrapped with steel wool, and is vertically placed on the surface of the gilded film. No pressure is applied in the vertical direction, and the weight is slid back and forth (reciprocal for one time) in the horizontal direction for 100 times. The sliding speed is 20-30 times / min (for example, 30 times / min), and the stroke is 100mm. The state of the surface of the gilded film is observed, and the hardness is tested using a pencil hardness tester according to the method in ASTM D3363.

[0105] 4. Cold-heat cycle: The glass product with a gilded film is placed in a high-low temperature alternating test chamber, and a cold-heat cycle test from -30°C (30 minutes) to 85°C (30 minutes) is performed. The temperature rising and falling rates are both 3°C / min, and a total of 20 cycles are performed. After the test is completed, the temperature is restored to room temperature, and the surface condition of the gilded film is observed.

[0106] Table 1 Test results of the performance of the gilded film on the surface of the glass product

[0107] From Table 1, it can be seen that the gilded film prepared by the present application has significantly better comprehensive performance than the gilded film prepared by the comparative examples. The electrochemical aluminum foil prepared by the adhesive in Comparative Example 3 cannot be directly gilded on the glass product. The comparison between Comparative Example 6 and the examples shows that the nano-material modified by the silane coupling agent plays a significant role in improving the scratch resistance. The comparison between Comparative Example 9 and the examples shows that the microcapsule curing agent plays an important role in ensuring the storage stability, construction period and deep curing of the adhesive layer. The comparison between Comparative Example 12 and the examples shows that the epoxy siloxane is the core component for realizing high-strength chemical bonding with glass, improving adhesion and durability.

[0108] The above examples are only preferred embodiments of the present application and are not intended to limit the protection scope of the present application. For any skilled person in the art, the present application can have various changes and variations. Any simple equivalent changes and modifications made according to the protection scope and content of the present application should be included in the protection scope of the present application.

Claims

1. An adhesive, characterized in that, The product comprises the following components in parts by weight: 15-30 parts of main resin, 5-10 parts of silane coupling agent modified nanomaterials, 10-20 parts of alicyclic epoxy resin, 0.5-2 parts of photocuring agent, and 2-5 parts of microencapsulated curing agent; wherein the main resin is any one of epoxy siloxane prepolymer, acrylated silane, or acrylated polyurethane.

2. The adhesive according to claim 1, characterized in that, The epoxy-based siloxane prepolymer is a product obtained by hydrolysis and condensation reaction of epoxy-based siloxane monomers (3-glycidyl etheroxypropyltriethoxysilane or γ-(2,3-epoxypropoxy)propyltrimethoxysilane), and the epoxy value of the product is 0.4~0.5 eq / 100g; or the acrylated silane is at least one of acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane; or the acrylated polyurethane is at least one of aliphatic polyurethane acrylate and aromatic polyurethane acrylate.

3. The adhesive according to claim 1, characterized in that, The nanomaterial is at least one of titanium dioxide nanowires, silicon dioxide nanotubes, boron nitride nanotubes, carbon nanotubes, and zinc oxide nanorods; or / and the silane coupling agent is at least one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane and acryloyloxypropyltrimethoxysilane.

4. The adhesive according to claim 1, characterized in that, The photocuring agent is a triarylthionium salt compound or a free radical photocuring agent; or / and the main component of the microcapsule-type curing agent is a eutectic mixture of dicyandiamide and urea or dicumyl peroxide.

5. The method for preparing the adhesive according to any one of claims 1 to 4, characterized in that, Includes the following steps: S1. The nanomaterial is placed in an acid solution and ultrasonically treated; the treated nanomaterial is reacted with an alcohol solution of the silane coupling agent at pH 4-5 and temperature 55-65℃. After the reaction is completed, the nanomaterial is centrifuged, washed, and dried to obtain the silane coupling agent modified nanomaterial. S2. Dissolve the main resin and alicyclic epoxy resin in an organic solvent, add the silane coupling agent-modified nanomaterials, and disperse them to a particle size D of the dispersion. 50 <150nm, then add the microcapsule curing agent, the light curing agent and the leveling agent, mix evenly and degas under vacuum to obtain the adhesive.

6. The preparation method according to claim 5, characterized in that, The silane coupling agent-modified nanomaterials described in step S2 were added in three batches, with a 5-minute interval between each addition. After each addition, the mixture was stirred at 1200 rpm for 15 minutes. Then, the resulting mixture was ground to a particle size D using a three-roll mill. 50 <150nm.

7. An electroplated aluminum foil, characterized in that, It includes an adhesive layer, which is prepared using the adhesive according to any one of claims 1 to 4.

8. The method for preparing the electroplated aluminum foil according to claim 7, characterized in that, Includes the following steps: The adhesive was applied to the metal layer using a microgravure coating method, and after being dried with hot air at a gradient temperature of 60°C to 80°C, it was irradiated with an irradiation dose of 300 to 400 mJ / cm under inert gas protection. 2 The adhesive layer is pre-cured under ultraviolet light and then wound up and cured to obtain the adhesive layer.

9. The method for hot stamping electroplated aluminum foil onto glass products as described in claim 7, characterized in that, The electroplated aluminum foil is directly hot-stamped onto the glass product under the following conditions: hot-stamping at 150℃~170℃ and 0.4~0.6MPa for 0.8~1.2 seconds. After hot stamping, place the glass product with the hot stamping film at 75℃~85℃ for 10~15 minutes for heat treatment.

10. A glass product with a hot stamping film, characterized in that, It is prepared by the method described in claim 9.

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