Preparation method of holographic layer, holographic IMR film, air conditioner holographic IMR panel and air conditioner

Abstract

The present invention provides a method for preparing a holographic layer, a holographic IMR film, a holographic IMR panel for an air conditioner, and an air conditioner, belonging to the field of in-mold decoration. The holographic layer preparation method comprises the following steps: preparing a cycloolefin copolymer and a maleic anhydride prepolymer; preparing a mixture of nano-zinc sulfide and vinyl acetate; and molding the holographic layer. The holographic layer material of the present invention exhibits excellent flatness, gloss, high light transmittance, and molding properties, and can be used in holographic IMR films, holographic IMR panels for air conditioners, and air conditioners.

Description

Technical Field

[0001] The present invention belongs to the field of in-mold decoration, and in particular relates to a method for preparing a holographic layer, a holographic IMR film, an air conditioner holographic IMR panel, and an air conditioner. Background Art

[0002] In-mold transfer (IMR) technology typically uses polyethylene terephthalate (PET) as the primary substrate, printing decorative patterns and various functional coatings onto the substrate. The roll is then fed into a specialized mold for injection molding using a precisely positioned film feeder. The pattern on the substrate is then transferred to the surface of the plastic part, integrating the decorative effect with the injection molding process. This allows for rich pattern effects and ease of replacement. Conventional IMR films consist of a substrate layer, release layer, protective layer, pattern layer, and adhesive layer. Because glossy or vibrant effects can quickly attract users, the introduction of holographic technology into IMR films—adding a holographic layer to conventional IMR films—helps enhance the product's appearance.

[0003] The holographic layer of an IMR film typically consists of a molded layer and an evaporated layer. The molded layer acts as a grating, recording information, while the evaporated layer primarily reflects and refracts. When light strikes the surface of the IMR film, the combined action of the molded layer's grating and the evaporated layer controls the light, resulting in a holographic effect. Therefore, the molded layer must have high transmittance to facilitate light penetration, while also possessing high heat resistance and toughness to facilitate high-temperature molding processes. The evaporated layer also requires a high refractive index and reflectivity. However, the commonly used polyethylene terephthalate (PET) substrate suffers from poor heat resistance, polymethyl methacrylate (PMMA) has high transmittance but poor toughness, and cyclic olefin copolymers have low surface energy and reactive inertness, making copolymerization and grafting with other polymers difficult. The evaporated layer is typically made of aluminum, but this is costly, complex, and can damage the substrate. Zinc sulfide, used as an evaporated layer, suffers from poor compatibility with the substrate. Summary of the Invention

[0004] In response to the above-mentioned problems existing in the prior art, the present invention proposes a method for preparing a holographic layer, a holographic IMR film, an air conditioner holographic IMR panel and an air conditioner, wherein the holographic layer material has excellent flatness, glossiness, high transmittance and moldability, realizes integrated molded molding, and has a simple preparation process and low industrial cost. It replaces the traditional molded process plus vapor deposition process, reducing the damage to the substrate caused by the vapor deposition process.

[0005] In order to achieve the above object, the present invention provides a method for preparing a holographic layer, comprising the following steps:

[0006] The cycloolefin copolymer and maleic anhydride prepolymer preparation steps include: pre-treating the cycloolefin copolymer film, coating it with a mixture of maleic anhydride and a photocatalyst, and then pre-polymerizing it under ultraviolet irradiation to prepare the cycloolefin copolymer and maleic anhydride prepolymer;

[0007] The steps of preparing the mixed solution of nano zinc sulfide and vinyl acetate are as follows: first preparing nano zinc sulfide particles, and then preparing the mixed solution of nano zinc sulfide and vinyl acetate;

[0008] Holographic layer molding preparation steps: coating a mixture of nano zinc sulfide and vinyl acetate on cycloolefin copolymer and maleic anhydride prepolymer, polymerizing them under ultraviolet light, then ultrasonically cleaning them with acetone, and molding them to prepare the holographic layer.

[0009] In some embodiments, in the step of preparing the cyclic olefin copolymer and the maleic anhydride prepolymer, the step of pretreating the cyclic olefin copolymer film is to soak the cyclic olefin copolymer film in an acetone solution at 40° C. to 60° C. for 10 min to 30 min.

[0010] In some embodiments, in the step of preparing the cycloolefin copolymer and the maleic anhydride prepolymer, the method for preparing the maleic anhydride and photocatalyst mixed solution comprises taking 50g to 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 1g to 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution. It is understood that according to actual conditions, those skilled in the art can adjust the amount of each component within the above range. For example, the amount of maleic anhydride can also be 50g, 100g, 150g, 200g, 250g, 300g, 350g or any point value within the above range, and the amount of benzophenone can also be 1g, 2g, 3g, 4g, 5g, 6g, 7g, 8g, 9g, 10g or any point value within the above range.

[0011] In some embodiments, in the step of preparing the cycloolefin copolymer and the maleic anhydride prepolymer, when the ultraviolet light is irradiated for prepolymerization, the ultraviolet light wavelength is set to 254 nm and the irradiation intensity is set to 6000 uW / cm 2 ~8000uW / cm 2 , the irradiation time is set to 3s~10s.

[0012] In some embodiments, in the step of preparing the mixed solution of nano zinc sulfide and vinyl acetate, the preparation method of the nano zinc sulfide particles includes: first weighing 408g of zinc chloride and 4056g of thiourea and adding them to a reactor, then adding 21000g of diethylenetriamine, stirring for 20 minutes, and then ultrasonically dispersing for 15 minutes, then stirring again for 20 minutes, heating to 160°C to 180°C, refluxing for 12 hours, washing with deionized water and anhydrous ethanol, centrifuging, and vacuum drying to obtain nano zinc sulfide particles.

[0013] In some embodiments, in the step of preparing the nano zinc sulfide and vinyl acetate mixed solution, 200g to 350g of nano zinc sulfide particles are taken, 300g to 450g of vinyl acetate and 1000g of xylene are added, and after ultrasonication for 15min to 20min, the mixture is stirred for 10min to 20min, and 5g to 15g of photoinitiator benzophenone is added while stirring to obtain a nano zinc sulfide and vinyl acetate mixed solution. It is understandable that those skilled in the art can adjust the amount of each component within the above range according to actual conditions. For example, the amount of nano zinc sulfide particles can also be 200g, 210g, 220g, 230g, 240g, 250g, 260g, 270g, 280g, 290g, 300g, 310g, 320g, 330g, 340g, 350g or any point value within the above range. The amount of vinyl acetate can also be 200g, 210g, 220g, 230g, 240g, 250g, 260g, 270g, 280g, 290g, 300g, 310g, 320g, 330g, 340g, 350g or any point value within the above range. The amount of benzophenone can be 300g, 310g, 320g, 330g, 340g, 350g, 360g, 370g, 380g, 390g, 400g, 410g, 420g, 430g, 440g, 450g or any point value within the above range. The amount of benzophenone can also be 5g, 6g, 7g, 8g, 9g, 10g, 11g, 12g, 13g, 14g, 15g or any point value within the above range.

[0014] In some embodiments, during the holographic layer molding preparation step, when the ultraviolet light is irradiated and polymerized, the ultraviolet light wavelength is set to 254 nm and the irradiation intensity is set to 6000 uW / cm 2 ~8000uW / cm 2 , the irradiation time is set to 10s~30s.

[0015] The present invention also provides a holographic IMR film, comprising a film layer, a release layer, a UV protective layer, a holographic layer, a logo layer, a protective layer, a pigment layer and an adhesive layer stacked in sequence, wherein the holographic layer is prepared by the above-mentioned holographic layer preparation method.

[0016] The present invention also provides an air conditioner holographic IMR panel, which is prepared by injection molding the above-mentioned holographic IMR film.

[0017] The present invention also provides an air conditioner, comprising the above-mentioned air conditioner holographic IMR panel.

[0018] Compared with the prior art, the advantages and positive effects of the present invention are:

[0019] 1. The present invention pre-polymerizes a cycloolefin copolymer film and maleic anhydride by ultraviolet irradiation grafting to form a molded layer, and then uses a mixture of nano-zinc sulfide and vinyl acetate as a reflective / refractive dielectric layer. The mixture is evenly coated on the pre-polymerized cycloolefin copolymer film, then subjected to ultraviolet irradiation polymerization, and molded into an integrated holographic layer. This replaces the traditional molding process plus evaporation process, reduces damage to the substrate caused by the evaporation process, and the resulting holographic layer material has excellent flatness, gloss, high light transmittance, and moldability.

[0020] 2. The present invention prepares a cycloolefin copolymer and a maleic anhydride prepolymer by pretreating the cycloolefin copolymer film, coating it with a mixture of maleic anhydride and a photocatalyst, and then subjecting it to ultraviolet light irradiation for prepolymerization. This overcomes the difficulty in grafting the cycloolefin copolymer into other polymers. Specifically, due to the low surface energy and reaction inertness of the cycloolefin copolymer, in the technical solution of the present invention, the cycloolefin copolymer film is first soaked in an acetone solution, which increases the surface roughness of the cycloolefin copolymer and facilitates the formation of grafting sites. Ultraviolet light is a high-energy light, and using ultraviolet light irradiation to initiate the polymerization reaction can effectively control the degree of polymerization, thereby having the advantages of high speed, economy, environmental protection, wide applicability, and gentle controllability.

[0021] 3. When preparing nano zinc sulfide particles according to the present invention, diethylenetriamine is added to increase the content of two-dimensional flaky zinc sulfide, thereby improving the refractive index / reflectivity. A mixed solution of nano zinc sulfide and vinyl acetate is prepared, and the vinyl acetate and nano zinc sulfide are mixed and coated. Since vinyl acetate contains unsaturated double bonds and has the ability to undergo addition reaction and polymerization reaction, it can be polymerized with maleic anhydride, thereby improving compatibility and binding force. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 A flow chart of the process for preparing a holographic layer provided in an embodiment of the present invention;

[0023] Figure 2 A schematic structural diagram of an IMR diaphragm provided in an embodiment of the present invention;

[0024] Among them, 1. Film layer, 2. Release layer, 3. UV protective layer, 4. Holographic layer, 5. Protective layer, 6. Pigment layer, 7. Adhesive layer. DETAILED DESCRIPTION

[0025] In order to be able to understand the features and technical contents of the embodiments of the present invention in more detail, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the embodiments described below are only part of the embodiments of the present invention, rather than all the embodiments of the present invention. In the following technical description, for the convenience of explanation, a plurality of details are provided to provide a full understanding of the disclosed embodiments. However, one or more embodiments can still be implemented without these details. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection requested by the present invention.

[0026] Embodiments of the present invention provide a method for preparing a holographic layer, a holographic IMR film, a panel, and an air conditioner. The method comprises pre-polymerizing a cycloolefin copolymer film and maleic anhydride by ultraviolet irradiation grafting to form a molded layer. A mixture of nano-zinc sulfide and vinyl acetate is used as a reflective / refractive dielectric layer. The mixture is evenly coated on the pre-polymerized cycloolefin copolymer film, then subjected to ultraviolet irradiation polymerization, and molded into a one-piece process to obtain a holographic layer. Ultraviolet irradiation graft polymerization has the advantages of fast reaction speed, simple operation, no damage to the substrate, and precise control of reaction time and area, making it suitable for surface modification of polymer substrates. The holographic layer material prepared by the technical solution of the present invention not only has excellent flatness, gloss, high transmittance, and moldability, but also achieves one-piece molded process. This method has a simple preparation process and low industrial cost, replacing the traditional molding and evaporation process, reducing damage to the substrate caused by the evaporation process.

[0027] The method for preparing the holographic layer of the present invention comprises the following steps:

[0028] Preparation steps of cyclic olefin copolymer and maleic anhydride prepolymer: a certain mass of cyclic olefin copolymer (COC) film is placed in an acetone solution at 40° C. to 60° C. and immersed for 10 min to 30 min for pretreatment;

[0029] Under light-proof conditions, 50 g to 350 g of maleic anhydride (MAH) and 1000 g of xylene were added, and 1 g to 10 g of benzophenone (BP) as a photoinitiator was added, and stirred until all were dissolved to obtain a mixed solution;

[0030] The mixed solution was evenly coated on the pretreated cycloolefin copolymer (COC) film and subjected to ultraviolet light irradiation grafting to obtain cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength was set to 254 nm and the irradiation intensity was set to 6000 uW / cm 2 ~8000uW / cm 2 , the irradiation time is set to 3s~10s;

[0031] Preparation steps of the nano zinc sulfide and vinyl acetate mixture: first weigh 408g zinc chloride (ZnCl2) and 4056g thiourea into a reactor, then add 21000g diethylenetriamine (DETA), stir for 20 minutes, and then ultrasonically disperse for 15 minutes, then stir again for 20 minutes, heat to 160℃~180℃, reflux for 12 hours, wash with deionized water and anhydrous ethanol, centrifuge, and vacuum dry to obtain nano zinc sulfide particles;

[0032] Take 200g-350g of the above-mentioned nano-zinc sulfide particles, add 300g-450g of vinyl acetate (VAc) and 1000g of xylene, ultrasonicate for 15min-20min, stir for 10min-20min, and add 5g-15g of photoinitiator benzophenone (BP) while stirring to obtain a mixture of nano-zinc sulfide and vinyl acetate;

[0033] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 1 to 5 minutes, and then molding to prepare a holographic layer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6000uW / cm 2 ~8000uW / cm 2 , the irradiation time is set to 10s~30s.

[0034] Cyclic olefin copolymer (COC) has advantages such as high light transmittance, high heat resistance, a relatively high glass transition temperature, high toughness, low density, and easy processing. The light transmittance of cyclic olefin copolymer (COC) is comparable to that of polymethyl methacrylate (PMMA), reaching over 92%. Its heat resistance is higher than that of polycarbonate (PC). Its glass transition temperature is between 100°C and 163°C. In the preparation steps of the cyclic olefin copolymer and maleic anhydride prepolymer of the present invention, the cyclic olefin copolymer (COC) used has a relatively high glass transition temperature, preferably between 150°C and 163°C. The maleic anhydride (MAH) used contains unsaturated double bonds and is an acid anhydride with extremely strong reactivity, and is commercially available.

[0035] The photoinitiator benzophenone (BP) belongs to the Norrish type II photoinitiator. Its initiation mechanism is as follows: under UV irradiation, benzophenone first transitions from the ground state to the singlet state ([BP]S), then to the triplet state ([BP]T) via intersystem crossing. After abstracting hydrogen atoms from the surface of the cycloolefin copolymer substrate, it generates surface free radicals and benzophenone semi-pinacol radicals. Surface free radicals can further initiate the graft polymerization of monomers, while semi-pinacol radicals, due to their benzene ring structure, create significant steric hindrance and are therefore unable to initiate chain propagation. Chain termination reactions primarily result from diradical termination between chain propagating radicals, between a chain propagating radical and a semi-pinacol radical, or between two semi-pinacol radicals. However, the diradical termination between a chain propagating radical and a semi-pinacol radical is a dormant species. Upon renewed light exposure, these dormant species break off and regenerate chain propagating radicals, which then continue to initiate chain propagation.

[0036] Zinc sulfide (ZnS) is a high-refractive-index crystal with a refractive index as high as 4.1 to 4.4. Zinc sulfide exhibits virtually no absorption in the visible light region and can be used to replace aluminum vapor-deposited layers to achieve refraction / reflection functions. In the preparation step of the nano-zinc sulfide and vinyl acetate mixture of the present invention, the addition of diethylenetriamine (DETA) can increase the content of two-dimensional flaky zinc sulfide, which contributes to improved refraction / reflectivity. Because vinyl acetate contains unsaturated double bonds and is capable of both addition and polymerization reactions, prepolymerization of a cycloolefin copolymer with maleic anhydride, followed by mixing and coating the vinyl acetate with nano-zinc sulfide particles and then polymerizing them with maleic anhydride, can enhance compatibility and bonding strength.

[0037] The present invention also provides a holographic IMR film, comprising a film layer, a release layer, a UV protective layer, a holographic layer, a protective layer, a pigment layer and an adhesive layer stacked in sequence, wherein the holographic layer is prepared using the above method, and the holographic layer is prepared through processes such as curing and drying to obtain the holographic IMR film.

[0038] The present invention also provides an air conditioner holographic IMR panel, which is prepared using the above-mentioned holographic IMR film. Specifically, the holographic IMR film is fed into a panel mold by a precisely positioned film feeding device for injection molding to prepare the air conditioner holographic IMR panel.

[0039] The present invention also provides an air conditioner, comprising the above-mentioned air conditioner holographic IMR panel.

[0040] In order to more clearly and in detail introduce the preparation method of the holographic layer, the holographic MIR film, the panel and the air conditioner provided by the embodiments of the present invention, they will be described below in conjunction with specific embodiments, wherein Table 1 is the raw material formula of Examples 1-6 and Comparative Examples 1-5, and Table 2 is the process conditions of the preparation method of Examples 1-6 and Comparative Examples 1-5.

[0041] Example 1

[0042] The method for preparing the holographic layer of this embodiment comprises the following steps:

[0043] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 40°C acetone solution for 30 minutes; taking 50g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 1g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6000uW / cm 2 , the irradiation time was set to 3s;

[0044] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 160° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 200 g of the above nano zinc sulfide particles are added, 300 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 15 minutes, stirred for 10 minutes, and 5 g of benzophenone as a photoinitiator is added while stirring to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0045] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, ultrasonic cleaning with acetone for 1 minute, and molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6000uW / cm 2 , the irradiation time was set to 10s.

[0046] Example 2

[0047] The method for preparing the holographic layer of this embodiment comprises the following steps:

[0048] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 150g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 3g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6400uW / cm 2 , the irradiation time was set to 5s;

[0049] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 163° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum-dried to obtain nano zinc sulfide particles; 220 g of the above nano zinc sulfide particles are added, 330 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 16 minutes, and then stirred for 12 minutes. While stirring, 7 g of benzophenone as a photoinitiator is added to obtain a mixed solution of nano zinc sulfide and vinyl acetate.

[0050] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, ultrasonic cleaning with acetone for 2 minutes, and molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6400uW / cm 2 , the irradiation time was set to 14s.

[0051] Example 3

[0052] The method for preparing the holographic layer of this embodiment comprises the following steps:

[0053] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 60°C acetone solution for 10 minutes; taking 200g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 5g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6900uW / cm 2 , the irradiation time was set to 7s;

[0054] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 167° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 250 g of the above nano zinc sulfide particles are added, 350 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 17 minutes, and then stirred for 14 minutes. While stirring, 9 g of benzophenone as a photoinitiator is added to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0055] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 3 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6900uW / cm 2 , the irradiation time was set to 17s.

[0056] Example 4

[0057] The method for preparing the holographic layer of this embodiment comprises the following steps:

[0058] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 250g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 7g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 7300uW / cm 2 , the irradiation time was set to 8s;

[0059] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21,000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 171° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum-dried to obtain nano zinc sulfide particles; 280 g of the above nano zinc sulfide particles are added, 380 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 18 minutes, and then stirred for 16 minutes. While stirring, 11 g of benzophenone as a photoinitiator is added to obtain a mixed solution of nano zinc sulfide and vinyl acetate.

[0060] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 4 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 7300uW / cm 2 , the irradiation time was set to 20s.

[0061] Example 5

[0062] The method for preparing the holographic layer of this embodiment comprises the following steps:

[0063] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 300g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 8g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 7600uW / cm 2 , the irradiation time was set to 9s;

[0064] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21,000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 175° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum-dried to obtain nano zinc sulfide particles; 320 g of the above nano zinc sulfide particles are added, 430 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 19 minutes, and then stirred for 18 minutes. While stirring, 13 g of a photoinitiator, benzophenone, is added to obtain a mixed solution of nano zinc sulfide and vinyl acetate.

[0065] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 5 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 7600uW / cm 2 , the irradiation time was set to 25s.

[0066] Example 6

[0067] The method for preparing the holographic layer of this embodiment comprises the following steps:

[0068] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 10s;

[0069] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 180° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 350 g of the above nano zinc sulfide particles are added, 450 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 20 minutes, stirred for 20 minutes, and 15 g of benzophenone as a photoinitiator is added while stirring to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0070] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 5 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 30s.

[0071] Comparative Example 1

[0072] The preparation method of the holographic layer of this comparative example comprises the following steps:

[0073] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 30°C acetone solution for 40 minutes; taking 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 10s;

[0074] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 180° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 350 g of the above nano zinc sulfide particles are added, 450 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 20 minutes, stirred for 20 minutes, and 15 g of benzophenone as a photoinitiator is added while stirring to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0075] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 5 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 30s.

[0076] Comparative Example 2

[0077] The preparation method of the holographic layer of this comparative example comprises the following steps:

[0078] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 40g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 10s;

[0079] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 min, ultrasonically dispersed for 15 min, and then stirred again for 20 min, refluxed at 180° C. for 12 h, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 350 g of the above nano zinc sulfide particles are added, 450 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 20 min, stirred for 20 min, and 15 g of benzophenone as a photoinitiator is added while stirring to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0080] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 5 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 30s.

[0081] Comparative Example 3

[0082] The preparation method of the holographic layer of this comparative example comprises the following steps:

[0083] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 10s;

[0084] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 min, ultrasonically dispersed for 15 min, and then stirred again for 20 min. The mixture is heated to 180° C., refluxed for 12 h, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 180 g of the above nano zinc sulfide particles is added, 450 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 20 min, stirred for 20 min, and 15 g of benzophenone as a photoinitiator is added while stirring to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0085] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 5 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 30s.

[0086] Comparative Example 4

[0087] The preparation method of the holographic layer of this comparative example comprises the following steps:

[0088] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6400uW / cm 2 , the irradiation time was set to 10s;

[0089] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 min, ultrasonically dispersed for 15 min, and then stirred again for 20 min. The mixture is heated to 163° C., refluxed for 12 h, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 220 g of the above nano zinc sulfide particles are added, 200 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 16 min, and then stirred for 12 min. While stirring, 15 g of a photoinitiator, benzophenone, is added to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0090] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, ultrasonic cleaning with acetone for 2 minutes, and molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6400uW / cm 2 , the irradiation time was set to 30s.

[0091] Comparative Example 5

[0092] The preparation method of the holographic layer of this comparative example comprises the following steps:

[0093] The preparation steps of the cycloolefin copolymer and maleic anhydride prepolymer are as follows: pre-treating the cycloolefin copolymer film by immersing it in a 50°C acetone solution for 20 minutes; taking 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 10g of photoinitiator benzophenone, and stirring until completely dissolved to obtain a mixed solution; uniformly coating the mixed solution on the pre-treated cycloolefin copolymer film, and performing ultraviolet light irradiation grafting to obtain the cycloolefin copolymer and maleic anhydride prepolymer, wherein the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 10s;

[0094] The steps of preparing a mixed solution of nano zinc sulfide and vinyl acetate are as follows: 408 g of zinc chloride and 4056 g of thiourea are weighed and added to a reactor, 21000 g of diethylenetriamine is added, the mixture is stirred for 20 minutes, ultrasonically dispersed for 15 minutes, and then stirred again for 20 minutes. The mixture is heated to 180° C., refluxed for 12 hours, washed with deionized water and anhydrous ethanol, centrifuged, and vacuum dried to obtain nano zinc sulfide particles; 350 g of the above nano zinc sulfide particles are added, 450 g of vinyl acetate and 1000 g of xylene are added, ultrasonically treated for 20 minutes, stirred for 20 minutes, and 15 g of benzophenone as a photoinitiator is added while stirring to obtain a mixed solution of nano zinc sulfide and vinyl acetate;

[0095] Holographic layer molding preparation steps: a mixture of nano zinc sulfide and vinyl acetate is evenly coated on the surface of cycloolefin copolymer and maleic anhydride prepolymer, and then subjected to ultraviolet light irradiation polymerization, followed by ultrasonic cleaning with acetone for 5 minutes, and then molding to prepare a holographic layer. The ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 8000uW / cm 2 , the irradiation time was set to 5s.

[0096] Table 1 Raw material formula of Examples 1-6 and Comparative Examples 1-5 (unit: g)

[0097]

[0098]

[0099] Table 2 Process conditions of Examples 1-6 and Comparative Examples 1-5

[0100]

[0101]

[0102] Performance Testing

[0103] The holographic layers obtained in Examples 1-6 and Comparative Examples 1-5 were cured and dried to produce holographic IMR films. The resulting holographic IMR films were evaluated for transmittance, gloss, adhesion, embossing performance, and holographic effect. The test standards are shown in Table 3, and the test results are shown in Table 4. For performance testing, transmittance was tested according to GB / T 2410, using a haze meter method. Transmittance is affected by various factors, including COC immersion time, UV grafting rate, zinc sulfide content, and UV polymerization rate. Gloss was tested according to GB / T 8807, using a 60° angle. Adhesion was tested according to GB / T 9286, using a cross-cut test and 3M tape. Embossing performance was primarily evaluated for integrity. Holographic effect was evaluated visually and subjectively.

[0104] Table 3 Holographic IMR film performance test standards

[0105] project Light transmittance Glossiness Adhesion Molding performance Holographic effect evaluation Test standards GB / T 2410 GB / T 8807 GB / T9286 / visual Test conditions Haze meter method 60° Cross-cut, 3M tape Check integrity Visual subjective evaluation

[0106] Table 4 Performance test results of holographic IMR films prepared from holographic layers of Examples 1-6 and Comparative Examples 1-5

[0107]

[0108]

[0109] As can be seen from the above, in Examples 1-6 of the present invention, a cycloolefin copolymer film and maleic anhydride are grafted under ultraviolet radiation for pre-polymerization to form a molding layer, a mixture of nano-zinc sulfide and vinyl acetate is used as a reflective / refractive dielectric layer, the mixture is uniformly coated on the pre-polymerized cycloolefin copolymer film, and then ultraviolet radiation polymerization is performed, and molding is integrated to obtain a holographic layer, and then the holographic layer is processed by printing and other processes to obtain a holographic IMR film, with a transmittance greater than 45, a gloss greater than 89, and a molding performance test showing complete grating transfer, no sticking to the board, adhesion level 0, and an excellent holographic effect. Comparative Examples 1-3 and 5 correspond to Example 6, wherein, unlike Example 6, the pretreatment immersion temperature of the cyclic olefin copolymer in Comparative Example 1 is lower than that in Example 6, and the immersion time is longer than that in Example 6. The light transmittance and glossiness of the holographic IMR film prepared from the obtained holographic layer are significantly lower than those in Example 6, and the grating transfer in the molding performance test is incomplete, sticking to the board, the adhesion is level 4, and the holographic effect is evaluated as poor. Unlike Example 6, the amount of maleic anhydride used in Comparative Example 2 is significantly less than that in Example 6. The light transmittance and glossiness of the holographic IMR film prepared from the obtained holographic layer are significantly lower than those in Example 6, and the grating transfer in the molding performance test is incomplete, sticking to the board, the adhesion is level 4, and the holographic effect is evaluated as poor. The grating transfer was incomplete, the plate stuck, the adhesion was level 3, and the holographic effect was evaluated as poor. Unlike Example 6, the amount of nano-zinc sulfide used in Comparative Example 3 was less than that in Example 6, and the light transmittance and glossiness of the holographic IMR film prepared by the resulting holographic layer were significantly lower than those in Example 6, and the holographic effect was evaluated as poor. Unlike Example 6, the irradiation time for ultraviolet light irradiation polymerization in the holographic layer molding preparation step in Comparative Example 5 was shorter than that in Example 6, and the light transmittance and glossiness of the holographic IMR film prepared by the resulting holographic layer were significantly lower than those in Example 6. In addition, the molding performance test showed incomplete grating transfer, the plate stuck, the adhesion was level 2, and the holographic effect was evaluated as poor.

[0110] Finally, it should be noted that the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only the better feasible embodiments of the present invention. The above-mentioned embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations, modifications, evolutions and improvements made by ordinary technicians in this field to the technical solutions of the present invention should fall within the scope of protection determined by the claims of the present invention.

Claims

1. A method for preparing a holographic layer, characterized in that: The following steps are involved: The cycloolefin copolymer and maleic anhydride prepolymer preparation steps include: pre-treating the cycloolefin copolymer film, coating it with a mixture of maleic anhydride and a photocatalyst, and then pre-polymerizing it under ultraviolet irradiation to prepare the cycloolefin copolymer and maleic anhydride prepolymer; The steps of preparing the mixed solution of nano zinc sulfide and vinyl acetate are as follows: first preparing nano zinc sulfide particles, and then preparing the mixed solution of nano zinc sulfide and vinyl acetate; Holographic layer molding preparation steps: coating a mixture of nano zinc sulfide and vinyl acetate on cycloolefin copolymer and maleic anhydride prepolymer, polymerizing them under ultraviolet light, then ultrasonically cleaning them with acetone, and molding them to prepare the holographic layer.

2. The method for preparing a holographic layer according to claim 1, characterized in that: In the step of preparing the cycloolefin copolymer and the maleic anhydride prepolymer, the step of pretreating the cycloolefin copolymer film is to soak the cycloolefin copolymer film in an acetone solution at 40° C. to 60° C. for 10 minutes to 30 minutes.

3. The method for preparing a holographic layer according to claim 1, characterized in that: In the step of preparing the cycloolefin copolymer and maleic anhydride prepolymer, the method for preparing the mixed solution of maleic anhydride and photocatalyst includes taking 50g to 350g of maleic anhydride and 1000g of xylene under light-proof conditions, adding 1g to 10g of benzophenone as a photoinitiator, and stirring until all are dissolved to obtain a mixed solution.

4. The method for preparing a holographic layer according to claim 1, wherein: In the step of preparing the cycloolefin copolymer and maleic anhydride prepolymer, when the ultraviolet light is irradiated for prepolymerization, the ultraviolet light wavelength is set to 254 nm and the irradiation intensity is set to 6000 uW / cm 2 ~8000uW / cm 2 , the irradiation time is set to 3s~10s.

5. The method for preparing a holographic layer according to claim 1, characterized in that: In the step of preparing the nano zinc sulfide and vinyl acetate mixed solution, the preparation method of the nano zinc sulfide particles includes: first weighing 408g of zinc chloride and 4056g of thiourea and adding them to a reaction kettle, then adding 21000g of diethylenetriamine, stirring for 20 minutes, then ultrasonically dispersing for 15 minutes, then stirring again for 20 minutes, heating to 160°C to 180°C, refluxing for 12 hours, washing with deionized water and anhydrous ethanol, centrifuging, and vacuum drying to obtain nano zinc sulfide particles.

6. The method for preparing a holographic layer according to claim 1, characterized in that: In the step of preparing the nano-zinc sulfide and vinyl acetate mixed solution, 200g to 350g of nano-zinc sulfide particles are taken, 300g to 450g of vinyl acetate and 1000g of xylene are added, and after ultrasonication for 15min to 20min, the mixture is stirred for 10min to 20min, and 5g to 15g of benzophenone as a photoinitiator is added while stirring to obtain the nano-zinc sulfide and vinyl acetate mixed solution.

7. The method for preparing a holographic layer according to claim 1, characterized in that: In the holographic layer molding preparation step, when ultraviolet light irradiation polymerization is performed, the ultraviolet light wavelength is set to 254nm and the irradiation intensity is set to 6000uW / cm 2 ~8000uW / cm 2 , the irradiation time is set to 10s~30s.

8. A holographic IMR film, characterized in that: The invention comprises a film layer, a release layer, a UV protection layer, a holographic layer, a logo layer, a protection layer, a pigment layer and an adhesive layer stacked in sequence, wherein the holographic layer is prepared by the preparation method of the holographic layer according to any one of claims 1 to 7.

9. An air conditioner holographic IMR panel, characterized in that: The holographic IMR film according to claim 8 is prepared by injection molding.

10. An air conditioner, characterized in that: The air conditioner holographic IMR panel comprises the one described in claim 9.

Images