High-refractive-index glue based on amino zirconium-based metal organic polyhedral dispersed zirconium dioxide, glue film and preparation method

Abstract

The invention discloses high-refractive-index glue based on amino zirconium-based metal organic polyhedral dispersed zirconium dioxide, a glue film and a preparation method. The high-refractive-index glue is prepared from the following raw material components in parts by weight: 100 parts of acrylate copolymer, 0.05 to 0.25 part of thermal curing agent, 0.2 to 2 parts of photoinitiator, 0.3 to 2.5 parts of photo-crosslinking agent and 10 to 30 parts of Zr-MOPs / ZrO2 dispersion liquid. In the Zr-MOPs / ZrO2 dispersion liquid, through an amino-containing zirconium-based metal organic polyhedron (Zr-MOP) in-situ anchoring technology, by utilizing strong chemical bonding between amino and the surfaces of nanoparticles and a steric hindrance effect of a Zr-MOP skeleton, uniform dispersion and long-acting stability of the nanoparticles are realized by a one-step method; meanwhile, the ultraviolet aging resistance of the glue can be improved through the free radical capturing capacity of the Zr-MOP ligand, a complex modification process or toxic additives are not needed, and an efficient and low-cost solution is provided for industrial application of the high-refractive-index glue.

Description

Technical Field

[0001] This invention relates to the field of adhesive materials, and in particular to a high refractive index adhesive, adhesive film, and preparation method based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide. Background Technology

[0002] High-refractive-index adhesives are widely used in various fields due to their excellent optical properties and bonding strength. In the manufacture of optical components, their high refractive index (e.g., 1.75 and above) can significantly reduce light reflection loss at the bonding interface, improving the light transmission efficiency of lenses, prisms, and fiber optic coupling devices. In display and touch technology, refractive index matching reduces glare and enhances the brightness and contrast of LCD panels and displays. Simultaneously, in high-power LED packaging, it can reduce total internal reflection and improve light extraction efficiency. In the manufacture of AR / VR lenses and micro / nano optical devices, it balances the requirements of high refractive index and light transmission to adapt to precision imprinting processes. Solar cell packaging utilizes its light-reflection-reducing properties to improve energy conversion efficiency. High-strength bonding of precision instruments, sensors, and dissimilar materials (such as glass and metal) relies on its mechanical stability and environmental resistance.

[0003] In existing high-refractive-index adhesives, zirconium dioxide nanoparticles are prone to uncontrolled aggregation due to their high surface energy, leading to a significant decrease in colloidal transmittance and noticeable performance degradation after long-term storage. Traditional dispersion techniques rely on multi-step surface modification, which is cumbersome and leaves residual modifiers that can cause yellowing or deterioration of interfacial compatibility. Furthermore, the weak interfacial bonding between nanoparticles and the matrix makes them susceptible to phase separation under long-term exposure to humid, hot, or ultraviolet environments, accelerating adhesive aging. Patent CN109971413A uses phase transfer technology, taking advantage of the greater solubility of phosphoric acid-coated zirconium dioxide nanoparticles in less polar solvents, to transfer nanoparticles dispersed in the aqueous phase to the organic phase, preparing a high-refractive-index composite encapsulating adhesive material. However, this method is relatively complex and relies solely on phosphoric acid modification, resulting in a high risk of particle aggregation after aging. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a high refractive index adhesive, adhesive film, and preparation method based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: In its first aspect, the present invention provides a high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide, comprising the following raw material components by weight:

[0006] 100 parts of acrylate copolymer, 0.05-0.25 parts of thermosetting agent, 0.2-2 parts of photoinitiator, 0.3-2.5 parts of photocrosslinking agent, and 10-30 parts of Zr-MOPs / ZrO2 dispersion;

[0007] The solid content of the Zr-MOPs / ZrO2 dispersion is 10%-20%.

[0008] Preferably, the Zr-MOPs / ZrO2 dispersion is prepared by the following method:

[0009] Zirconium source, organic ligand, ZrO2 nanoparticles, deionized water and a first solvent are mixed. The resulting solution is reacted under heating and microwave action. After the reaction is completed, the mixture is filtered. The solid product is washed with the first solvent and then the solid content is adjusted to 10%-20% with the first solvent to obtain the Zr-MOPs / ZrO2 dispersion.

[0010] Preferably, the zirconium source is selected from at least one of zirconium dichloride (ZrCl2), zirconium oxychloride (ZrOCl2·8H2O), and zirconium nitrate (Zr(NO3)4);

[0011] The organic ligand is selected from at least one of 2-aminoterephthalic acid (NH2-BDC), terephthalic acid (BDC), biphenyl dimethyl phthalate (BPDC), and NH2-BDC;

[0012] The first solvent is selected from at least one of DMA, NMP or DMF.

[0013] Preferably, the Zr-MOPs / ZrO2 dispersion is prepared by the following method:

[0014] 0.025-0.1 mmol zirconium source, 0.02-0.09 mmol organic ligand, 0.01-0.05 g ZrO2 nanoparticles, deionized water and a first solvent were mixed. The resulting solution was reacted under microwave irradiation at 80-120 °C and 500-1000 W for 2-5 minutes. After the reaction was completed, the mixture was filtered. The solid product was washed with the first solvent and then the solid content was adjusted to 10%-20% with the first solvent to obtain the Zr-MOPs / ZrO2 dispersion.

[0015] The particle size of the nano ZrO2 particles is 2-20 nm.

[0016] Preferably, the raw materials for preparing the acrylate polymer include, by weight, 35-150 parts of hard monomer, 15-70 parts of soft monomer, 4-20 parts of functional monomer, 0.05-0.3 parts of initiator, 40-160 parts of second solvent and 0.05-0.2 parts of polymerization inhibitor.

[0017] Preferably, the acrylate polymer is prepared from hard monomer 75, soft monomer 35, functional monomer 8, initiator 0.15, second solvent 80 and polymerization inhibitor 0.1.

[0018] Preferably, the hard monomer is selected from one or more of phenyl methacrylate, benzyl methacrylate, naphthyl acrylate, styrene, adamantyl acrylate, isobornyl methacrylate, norbornyl acrylate, phenyl sulfide methacrylate, and thiophene acrylate.

[0019] The soft monomer is selected from one or more of butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, octadecyl acrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

[0020] The functional monomer is selected from one or more of glycidyl methacrylate, acrylic acid, acrylamide, maleic anhydride, hexafluorobutyl methacrylate, and vinyltrimethoxysilane.

[0021] The initiator is selected from one or more of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, dicumyl peroxide, and tert-butyl peroxide;

[0022] The second solvent is selected from one or more of N,N-dimethylacetamide, toluene, ethyl acetate, N-methylpyrrolidone, and tetrahydrofuran;

[0023] The polymerization inhibitor is selected from one or more of p-benzoquinone, hydroquinone, 4-methoxyphenol, phenothiazine, 2,2,6,6-tetramethylpiperidine-1-oxy, and sodium nitrite.

[0024] Preferably, the acrylate polymer is prepared by the following steps:

[0025] Hard monomer, soft monomer, functional monomer, and second solvent are added to a reaction vessel, heated to 50-65℃, and stirred under nitrogen for 30 minutes. The initiator is added to the reaction vessel in three portions, with an interval of 20 minutes between each addition. The reaction temperature is controlled at 65-75℃, and the reaction is carried out for 6-8 hours. An inhibitor is added to terminate the reaction. The reaction product is poured into cold methanol to precipitate the polymer. After filtration and drying, the acrylate polymer is obtained.

[0026] A second aspect of the present invention provides a method for preparing a high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide as described above, comprising the following steps: mixing 100 parts by weight of acrylate copolymer, 0.05-0.25 parts by thermosetting agent, 0.2-2 parts by photoinitiator, 0.3-2.5 parts by photocrosslinking agent, and 10-30 parts by weight of Zr-MOPs / ZrO2 dispersion, stirring evenly to obtain the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide;

[0027] The thermosetting agent is selected from one or more of the following diisocyanates: toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, and isophorone diisocyanate curing agents;

[0028] The photoinitiator is selected from one or more of the following high-efficiency photoinitiators: 2,4,6-trimethylbenzoyl (TPO), 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173), 1-hydroxycyclohexylphenyl ketone (photoinitiator 184), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), bibenzoyl (photoinitiator 651), and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (photoinitiator 907).

[0029] The photocrosslinking agent is selected from one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and hexanediol diacrylate.

[0030] In a third aspect, the present invention provides a high refractive index adhesive film, which is prepared by the following method: uniformly coating the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide as described above onto a heavy release film, baking at 100-150°C for 1.5-6 min to obtain an adhesive layer with a thickness of 25-100 μm, attaching a light release film onto the adhesive surface, and curing to obtain the high refractive index adhesive film.

[0031] The beneficial effects of this invention are:

[0032] 1. This invention provides a high refractive index adhesive, adhesive film, and preparation method based on amino-zirconium-based metal-organic polyhedrons (Zr-MOPs) dispersed zirconium dioxide. In the Zr-MOPs / ZrO2 dispersion of this invention, the in-situ anchoring technology of amino-containing zirconium-based metal-organic polyhedra (Zr-MOPs) utilizes the strong chemical bonding between amino groups and the surface of nanoparticles and the steric hindrance effect of the Zr-MOP framework to achieve uniform dispersion and long-term stability of nanoparticles in one step. At the same time, the free radical scavenging ability of Zr-MOP ligands can improve the UV aging resistance of the adhesive. No complex modification process or toxic additives are required, providing an efficient and low-cost solution for the industrial application of high refractive index adhesives.

[0033] 2. This invention achieves efficient dispersion and long-term stability of nano-zirconium dioxide (ZrO2):

[0034] This invention overcomes the problem of easy aggregation of traditional nanoparticles, and the ZrO2 dispersed particle size is stable at 8-10nm (D50), with a particle size change of <10% after 30 days of storage and a light transmittance of ≥90%.

[0035] It is mainly achieved through the following mechanisms and methods:

[0036] (1) In-situ anchoring: ZrO2 nanoparticles are introduced simultaneously during the synthesis of Zr-MOPs, and strong chemical bonds are formed between amino groups (-NH2) and hydroxyl groups (-OH) on the surface of ZrO2 to avoid physical adsorption and desorption.

[0037] (2) Spatial steric hindrance effect: Zr-MOPs porous framework encapsulates ZrO2 particles, physically blocking the aggregation caused by van der Waals forces;

[0038] (3) One-step process: eliminates the traditional multi-step modification (such as silane coupling → washing → phase transfer), reducing process fluctuations.

[0039] 3. This invention achieves a synergistic improvement in refractive index and light transmittance:

[0040] When the ZrO2 addition amount reaches 5-10wt%, the refractive index of the adhesive is ≥1.70 and the light transmittance is ≥90%, which breaks through the limitation of the sharp decrease in light transmittance under traditional high filler load.

[0041] It is mainly achieved through the following mechanisms and methods:

[0042] (1) Refractive index superposition effect: Zr-MOP (n≈1.8) and ZrO2 (n≈2.1) form a gradient refractive structure, which reduces light scattering;

[0043] (2) Precise particle size control: The MOP framework restricts the growth of ZrO2, ensuring that the size of nanoparticles is ≤10nm (far smaller than the wavelength of visible light, Rayleigh scattering is negligible);

[0044] No impurity residue: In-situ synthesis avoids optical defects introduced by traditional modifiers (such as silane, PMMA coating layer).

[0045] 4. This invention simplifies the preparation process and reduces costs.

[0046] This invention can reduce the ZrO2 dispersion process from the traditional 3-5 steps to 1 step, reduce production costs by 30%-50%, and eliminate the need for complex equipment (such as centrifuges and multiple washing processes).

[0047] It is mainly achieved through the following mechanisms and methods:

[0048] (1) Microwave-assisted in-situ synthesis: Zr-MOPs are generated and dispersed in ZrO2 in a single reaction system, with a reaction time ≤5 minutes;

[0049] (2) Solvent recycling: DMA is used as the reaction solvent and can be directly used for subsequent glue preparation without the need to replace the solvent;

[0050] (3) No surface modification required: By replacing silane coupling agents with Zr-MOPs framework, the types of raw materials are reduced (saving more than 50% of the cost of auxiliary agents). Detailed Implementation

[0051] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0052] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0053] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0054] This invention provides a high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide, comprising the following raw material components in parts by weight:

[0055] 100 parts of acrylate copolymer, 0.05-0.25 parts of thermosetting agent, 0.2-2 parts of photoinitiator, 0.3-2.5 parts of photocrosslinking agent, and 10-30 parts of Zr-MOPs / ZrO2 dispersion;

[0056] The solid content of the Zr-MOPs / ZrO2 dispersion is 10%-20%.

[0057] In a preferred embodiment, the Zr-MOPs / ZrO2 dispersion was prepared by the following method:

[0058] Zirconium source, organic ligand, ZrO2 nanoparticles, deionized water and first solvent are mixed. The resulting solution is reacted under heating and microwave action. After the reaction is completed, the mixture is filtered. The solid product is washed with the first solvent and then the solid content is adjusted to 10%-20% with the first solvent to obtain Zr-MOPs / ZrO2 dispersion.

[0059] In a preferred embodiment, the zirconium source is selected from at least one of zirconium dichloride (ZrCl2), zirconium oxychloride (ZrOCl2·8H2O), and zirconium nitrate (Zr(NO3)4); more preferably, it is ZrCl2.

[0060] In a preferred embodiment, the organic ligand is selected from at least one of 2-aminoterephthalic acid (NH2-BDC), terephthalic acid (BDC), and biphenyl dimethyl phthalate (BPDC); more preferably, it is NH2-BDC.

[0061] In a preferred embodiment, the first solvent is selected from at least one of DMA (dimethylamine), NMP (N-methylpyrrolidone), or DMF (N,N-dimethylformamide).

[0062] In a preferred embodiment, the Zr-MOPs / ZrO2 dispersion was prepared by the following method:

[0063] 0.025-0.1 mmol zirconium source, 0.02-0.09 mmol organic ligand, 0.01-0.05 g ZrO2 nanoparticles, deionized water and a first solvent were mixed. The resulting solution was reacted at 80-120 °C and 500-1000 W under microwave irradiation for 2-5 minutes. After the reaction was completed, the mixture was filtered. The solid product was washed with the first solvent and then the solid content was adjusted to 10%-20% with the first solvent to obtain a Zr-MOPs / ZrO2 dispersion.

[0064] The nano-ZrO2 particles have a particle size of 2-20 nm, preferably 8 nm, and a surface hydroxyl density ≥3OH / nm. 2 .

[0065] In a preferred embodiment, the raw materials for preparing the acrylate polymer include, by weight, 35-150 parts of hard monomer, 15-70 parts of soft monomer, 4-20 parts of functional monomer, 0.05-0.3 parts of initiator, 40-160 parts of second solvent, and 0.05-0.2 parts of polymerization inhibitor.

[0066] In a preferred embodiment, the acrylate polymer is prepared from hard monomer 75, soft monomer 35, functional monomer 8, initiator 0.15, second solvent 80 and polymerization inhibitor 0.1.

[0067] The hard monomer is a high-refractive-index monomer containing an aromatic ring, a polycyclic ring, or sulfur. In a preferred embodiment, the hard monomer is selected from one or more of phenyl methacrylate, benzyl methacrylate, naphthyl acrylate, styrene, adamantane acrylate, isobornyl methacrylate, norbornyl acrylate, phenyl sulfide methacrylate, and thiophene acrylate.

[0068] The soft monomer is an acrylate monomer. In a preferred embodiment, the soft monomer is selected from one or more of butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, octadecyl acrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

[0069] In a preferred embodiment, the functional monomer is selected from one or more of glycidyl methacrylate, acrylic acid, acrylamide, maleic anhydride, hexafluorobutyl methacrylate, and vinyltrimethoxysilane.

[0070] In a preferred embodiment, the initiator is selected from one or more of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, diisopropylbenzene peroxide, and tert-butyl peroxide.

[0071] In a preferred embodiment, the second solvent is selected from one or more of N,N-dimethylacetamide, toluene, ethyl acetate, N-methylpyrrolidone, and tetrahydrofuran.

[0072] In a preferred embodiment, the polymerization inhibitor is selected from one or more of p-benzoquinone, hydroquinone, 4-methoxyphenol, phenothiazine, 2,2,6,6-tetramethylpiperidin-1-oxy, and sodium nitrite.

[0073] In a preferred embodiment, the acrylate polymer is prepared by the following steps:

[0074] Hard monomer, soft monomer, functional monomer, and second solvent are added to a reaction vessel. The temperature is raised to 50-65℃ and nitrogen gas is introduced and stirred for 30 minutes. The initiator is added to the reaction vessel in three portions, with an interval of 20 minutes between each addition. The reaction temperature is controlled at 65-75℃ and the reaction is carried out for 6-8 hours. The polymerization inhibitor is added to terminate the reaction. The reaction product is poured into cold methanol to precipitate the polymer. After filtration and drying, the acrylate polymer is obtained.

[0075] In a preferred embodiment, the thermosetting agent is selected from one or more of the following diisocyanates: toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, and isophorone diisocyanate curing agents.

[0076] In a preferred embodiment, the photoinitiator is selected from one or more of the following high-efficiency photoinitiators: 2,4,6-trimethylbenzoyl (TPO), 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173), 1-hydroxycyclohexylphenyl ketone (photoinitiator 184), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), bibenzoyl (photoinitiator 651), and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (photoinitiator 907).

[0077] In a preferred embodiment, the photocrosslinking agent is selected from one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and hexanediol diacrylate.

[0078] The present invention also provides a method for preparing the above-mentioned high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide, comprising the following steps: mixing 100 parts by weight of acrylate copolymer, 0.05-0.25 parts by thermosetting agent, 0.2-2 parts by photoinitiator, 0.3-2.5 parts by photocrosslinking agent, and 10-30 parts by weight of Zr-MOPs / ZrO2 dispersion, stirring evenly to obtain the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide;

[0079] The present invention also provides a high refractive index adhesive film, characterized in that it is prepared by the following method: the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide is uniformly coated on a heavy release film, baked at 100-150℃ for 1.5-6 min to obtain an adhesive layer with a thickness of 25-100 μm, a light release film is attached to the adhesive surface, and cured to obtain a high refractive index adhesive film.

[0080] In a preferred embodiment, the high refractive index adhesive film is prepared by the following method: the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide is uniformly coated on a 75 μm thick heavy release film, baked at 120°C for 3 min to obtain an adhesive layer with a thickness of 50 μm, a 50 μm thick light release film is attached to the adhesive surface, and cured at 55°C for three days to obtain the high refractive index adhesive film.

[0081] In this invention, by adjusting the ratio of hard monomers, functional monomers, and Zr-MOPs / ZrO2 dispersion, the refractive index of the OCA film is controlled to be above 1.65, more preferably above 1.7, while simultaneously meeting the requirements of transmittance ≥90% and haze <0.5. This allows the film to maintain high transmittance while possessing a high refractive index. The peel strength of the resulting film must be ≥1500 gf / inch, and the transmittance reduction must be <3% during damp heat aging (double 85, 500h); the yellowing index ΔYI must be <2 during ultraviolet aging (QUV, 1000h); and the particle size change must be <10% during ZrO2 dispersion stability (30 days).

[0082] In this invention, nano-sized ZrO2 particles are simultaneously introduced during the synthesis of Zr-MOPs. The amino group (-NH2) of the organic ligand (2-aminoterephthalic acid) forms strong chemical bonds (such as hydrogen bonds or coordination bonds) with the hydroxyl groups (-OH) on the ZrO2 surface. Simultaneously, the nanoparticles are physically isolated through the steric hindrance effect of the porous framework of the MOP. Traditional silane coupling or polymer coating requires multiple steps (dispersion → modification → phase transfer), and residual modifiers cause a decrease in transmittance; this invention overcomes these shortcomings.

[0083] This invention achieves the synergistic effect of chemical anchoring and physical barrier in a one-step process, without the need for additional surface modification. The ZrO2 particle size is stabilized at 8-10nm (DLS test), and the dispersion uniformity is improved by more than 80%.

[0084] The above is the general concept of the present invention. Based on this, detailed embodiments and comparative examples are provided below to further illustrate the present invention.

[0085] Preparation Example

[0086] Acrylate polymers and Zr-MOPs / ZrO2 dispersions were prepared in advance according to the following method for use in the examples and comparative examples.

[0087] 1. Acrylic ester polymer, the preparation method of which is as follows:

[0088] 60 parts by weight of phenyl methacrylate, 15 parts by weight of adamantyl acrylate, 25 parts by weight of butyl acrylate, 8 parts by weight of glycidyl methacrylate, 10 parts by weight of isooctyl acrylate, and 80 parts by weight of N,N-dimethylacetamide solvent were added to a reactor. The temperature was raised to 60°C, nitrogen gas was introduced, and the mixture was stirred for 30 minutes. 0.15 parts by weight of azobisisobutyronitrile (0.05 parts by weight) of initiator were added in three batches at 20-minute intervals. The reaction temperature was controlled at 70±2°C, and the reaction was continued for 6-8 hours. 0.1 parts by weight of p-benzoquinone polymerization inhibitor was added to terminate the reaction. The reaction product was poured into cold methanol to precipitate the polymer. After filtration, the polymer was vacuum dried at 60°C for 24 hours to obtain a transparent solid polymer with a molecular weight of 20,000-50,000 g / mol (PDI≤1.5).

[0089] 2. Zr-MOPs / ZrO2 dispersion, its preparation method is as follows:

[0090] ZrCl2 (0.105 g, 0.05 mmol), NH2-BDC (0.025 g, 0.045 mmol), and ZrO2 nanoparticles (0.03 g, 8 nm) were added to a polytetrafluoroethylene (PTFE) reactor, followed by 12 drops of deionized water and 1.5 mL of DMA. The PTFE reactor was then placed in a microwave reactor and reacted at 500 W and 80 °C for 5 minutes to generate a Zr-MOPs / ZrO2 composite. The resulting yellow crystals were filtered, washed three times with DMA, and the solid content of the product was adjusted to 15% with DMA to obtain the final product.

[0091] Zr-MOPs / ZrO2 dispersion.

[0092] Example 1

[0093] A high refractive index adhesive film is prepared by the following method:

[0094] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI (hexamethylene diisocyanate), 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 10 parts of...

[0095] The Zr-MOPs / ZrO2 dispersion was uniformly mixed to obtain a high refractive index adhesive based on aminozirconium-based metal-organic polyhedron dispersed zirconium dioxide (hereinafter referred to as high refractive index adhesive);

[0096] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0097] Example 2

[0098] A high refractive index adhesive film is prepared by the following method:

[0099] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 15 parts of Zr-MOPs / ZrO2 dispersion are uniformly mixed to obtain a high refractive index adhesive.

[0100] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0101] Example 3

[0102] A high refractive index adhesive film is prepared by the following method:

[0103] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 20 parts of Zr-MOPs / ZrO2 dispersion are uniformly mixed to obtain a high refractive index adhesive.

[0104] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0105] Example 4

[0106] A high refractive index adhesive film is prepared by the following method:

[0107] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 25 parts of Zr-MOPs / ZrO2 dispersion are uniformly mixed to obtain a high refractive index adhesive.

[0108] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0109] Example 5

[0110] A high refractive index adhesive film is prepared by the following method:

[0111] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 30 parts of Zr-MOPs / ZrO2 dispersion are uniformly mixed to obtain a high refractive index adhesive.

[0112] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0113] Comparative Example 1

[0114] A high refractive index adhesive film is prepared by the following method:

[0115] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 20 parts of ZrO2 dispersion (ultrasonic mixing) are uniformly mixed to obtain a high refractive index adhesive.

[0116] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0117] The ZrO2 dispersion was prepared by adding nano-zirconia powder (ZrO2, 2.25 g, average particle size 8 nm) and N,N-dimethylacetamide (DMA, 12.75 mL) into a 250 mL polytetrafluoroethylene reactor, mechanically stirring (500 rpm) for 30 minutes, and then ultrasonically treating it for 1 hour (2 seconds working / 1 second intermittent) in an ultrasonic cell disruptor at 800 W power and ice-water bath temperature control (≤25℃) to obtain an unmodified ZrO2 dispersion with a solid content of 15%.

[0118] Comparative Example 2

[0119] A high refractive index adhesive film is prepared by the following method:

[0120] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 20 parts of ZrO2 dispersion (KH570 modified) are uniformly mixed to obtain a high refractive index adhesive.

[0121] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0122] The ZrO2 dispersion was prepared by adding nano-zirconia powder (ZrO2, 2.25 g) to a mixed solution consisting of anhydrous ethanol (21.6 mL), deionized water (2.7 mL), and KH570 silane coupling agent (0.225 g, accounting for 10% of the ZrO2 mass). Acetic acid was added dropwise to adjust the pH to 4.5. The mixture was then magnetically stirred at 40 °C for 30 minutes to complete silane hydrolysis. Subsequently, the mixture was refluxed at 75 °C for 4 hours to achieve surface grafting. The reaction solution was centrifuged (8000 rpm, 15 minutes), washed three times with ethanol, and then vacuum dried at 60 °C for 6 hours. Finally, the modified powder was redispersed in DMA (12.75 mL) and ultrasonically treated (400 W, 30 minutes) to obtain a KH570 modified ZrO2 dispersion with a solid content of 15%.

[0123] Comparative Example 3

[0124] A high refractive index adhesive film is prepared by the following method:

[0125] By weight, 100 parts of acrylate polymer, 0.02 parts of HDI, 0.3 parts of photoinitiator 184, 0.5 parts of trimethylolpropane triacrylate, and 20 parts of ZrO2 dispersion (PMMA coated) are uniformly mixed to obtain a high refractive index adhesive.

[0126] High refractive index adhesive was coated onto a 75μm heavy release film and baked in an oven at 120℃ for 3 minutes to obtain an adhesive layer with a thickness of 100μm. A 50μm light release film was then bonded onto the adhesive surface and cured at 55℃ for 3 days to obtain a high refractive index adhesive film.

[0127] The ZrO2 dispersion was prepared by adding nano-zirconia powder (ZrO2, 2.25 g) and PMMA-co-MAA polymer (0.3375 g, accounting for 15% of the ZrO2 mass) together to toluene (22.05 mL). Pre-adsorption was completed by mechanical stirring at 60°C (400 rpm) for 12 hours. Subsequently, the mixture was refluxed at 110°C for 8 hours to achieve polymer anchoring and coating. After centrifuging (6000 rpm, 10 minutes) to remove agglomerates, the mixture was concentrated by rotary evaporation (60°C) and replaced with DMA solvent. The volume was then adjusted to 15 g to obtain a PMMA-coated ZrO2 dispersion with a solid content of 15%.

[0128] The high refractive index films obtained above were subjected to the following performance tests.

[0129] (1) Peel strength: Peel off the release film and attach it to a 0.05 mm transparent PET film. Cut the film into samples with a width of 25.4 mm and a length of 300 mm. Roll the sample onto a SUS 304 steel plate at a speed of 600 mm / min using a 2 kg roller. Let it stand for 20 min. Use a tensile testing machine to test its 180° peel adhesion. The specific test method refers to the ASMTD3330 international standard.

[0130] (2) Refractive index: The refractive index of the optical resin was tested using an elliptic polarization spectrometer.

[0131] (3) Transmittance and haze: In accordance with JIS K-7105 standard, the transmittance and haze of the optical film were measured using the transmitted light method with a Japanese Densho NDH 2000N haze meter.

[0132] (4) Resistance to damp heat aging: Place the sample in an aging chamber at a temperature of 85℃±2℃ and a humidity of 85%±5% for 500 hours. After the end of the aging process, test the change in transmittance. The sample is considered qualified if the transmittance decreases by less than 3% after aging.

[0133] (5) Ultraviolet aging: Using UVA-340 lamps (simulating the solar ultraviolet band 315-400nm), the irradiation intensity is 0.68W / m. 2 Cycle: 8 hours of UV irradiation (60℃) + 4 hours of condensation (50℃), total duration 1000 hours. After completion, the yellowing index is tested. Yellowing index ΔYI < 2 is considered qualified.

[0134] (6) Dispersion stability of ZrO2: The initial particle size distribution (D50≤10nm) was measured using a dynamic light scattering instrument (DLS); after storage for 30 days, the particle size change rate was retested and should be <10%; the colloidal sedimentation was observed (no stratification was acceptable).

[0135] The test results are shown in Table 1 below:

[0136] Table 1

[0137]

[0138] The test results show that the high refractive index films prepared in the embodiments of the present invention all meet the characteristics of high transmittance, low haze, and high refractive index.

[0139] Examples 1-5 show that by changing the proportion of added ZrO2 nanoparticles, the refractive index of the cured film was adjusted. As the proportion increased, the refractive index of the film showed an upward trend. In stability tests, after 500 hours of humid heat aging at 85°C, the transmittance decreased by less than 3%; after 1000 hours of UV aging, the yellowing index ΔYI was less than 2; and after 30 days of storage, the particle size change rate was less than 10%.

[0140] Comparative Examples 1-3 used traditional methods to modify or disperse ZrO2 nanoparticles. Although this improved the refractive index of the films, the transmittance was low and the haze was too high. In the stability test, none of Comparative Examples 1-3 met the test requirements.

[0141] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A high-refractive-index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide, characterized in that, Includes the following raw material components by weight: 100 parts of acrylate copolymer, 0.05-0.25 parts of thermosetting agent, 0.2-2 parts of photoinitiator, 0.3-2.5 parts of photocrosslinking agent, and 10-30 parts of Zr-MOPs / ZrO2 dispersion; The solid content of the Zr-MOPs / ZrO2 dispersion is 10%-20%.

2. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 1, characterized in that, The Zr-MOPs / ZrO2 dispersion was prepared by the following method: Zirconium source, organic ligand, ZrO2 nanoparticles, deionized water and a first solvent are mixed. The resulting solution is reacted under heating and microwave action. After the reaction is completed, the mixture is filtered. The solid product is washed with the first solvent and then the solid content is adjusted to 10%-20% with the first solvent to obtain the Zr-MOPs / ZrO2 dispersion.

3. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 2, characterized in that, The zirconium source is selected from at least one of zirconium dichloride, zirconium oxychloride, and zirconium nitrate. The organic ligand is selected from at least one of 2-aminoterephthalic acid, terephthalic acid, and biphenyl acid; The first solvent is selected from at least one of DMA, NMP or DMF.

4. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 3, characterized in that, The Zr-MOPs / ZrO2 dispersion was prepared by the following method: 0.025-0.1 mmol zirconium source, 0.02-0.09 mmol organic ligand, 0.01-0.05 g ZrO2 nanoparticles, deionized water and a first solvent were mixed. The resulting solution was reacted under microwave irradiation at 80-120 °C and 500-1000 W for 2-5 minutes. After the reaction was completed, the mixture was filtered. The solid product was washed with the first solvent and then the solid content was adjusted to 10%-20% with the first solvent to obtain the Zr-MOPs / ZrO2 dispersion. The particle size of the nano ZrO2 particles is 2-20 nm.

5. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 1, characterized in that, The raw materials for preparing the acrylate polymer, by weight, include: 35-150 parts of hard monomer, 15-70 parts of soft monomer, 4-20 parts of functional monomer, 0.05-0.3 parts of initiator, 40-160 parts of second solvent, and 0.05-0.2 parts of polymerization inhibitor.

6. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 5, characterized in that, The acrylate polymer is prepared from hard monomer 75, soft monomer 35, functional monomer 8, initiator 0.15, second solvent 80 and polymerization inhibitor 0.

1.

7. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 6, characterized in that, The hard monomer is selected from one or more of phenyl methacrylate, benzyl methacrylate, naphthyl acrylate, styrene, adamantane acrylate, isobornyl methacrylate, norbornyl acrylate, phenyl sulfide methacrylate, and thiophene acrylate. The soft monomer is selected from one or more of butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, octadecyl acrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate. The functional monomer is selected from one or more of glycidyl methacrylate, acrylic acid, acrylamide, maleic anhydride, hexafluorobutyl methacrylate, and vinyltrimethoxysilane. The initiator is selected from one or more of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, dicumyl peroxide, and tert-butyl peroxide; The second solvent is selected from one or more of N,N-dimethylacetamide, toluene, ethyl acetate, N-methylpyrrolidone, and tetrahydrofuran; The polymerization inhibitor is selected from one or more of p-benzoquinone, hydroquinone, 4-methoxyphenol, phenothiazine, 2,2,6,6-tetramethylpiperidine-1-oxy, and sodium nitrite.

8. The high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersion of zirconium dioxide according to claim 6, characterized in that, The acrylate polymer is prepared by the following steps: Hard monomer, soft monomer, functional monomer, and second solvent are added to a reaction vessel, heated to 50-65℃, and stirred under nitrogen for 30 minutes. The initiator is added to the reaction vessel in three portions, with an interval of 10-40 minutes between each addition. The reaction temperature is controlled at 65-75℃, and the reaction is carried out for 6-8 hours. An inhibitor is added to terminate the reaction. The reaction product is poured into cold methanol to precipitate the polymer. After filtration and drying, the acrylate polymer is obtained.

9. A method for preparing a high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide as described in any one of claims 1-8, characterized in that, The process includes the following steps: by weight, 100 parts of acrylate copolymer, 0.05-0.25 parts of thermosetting agent, 0.2-2 parts of photoinitiator, 0.3-2.5 parts of photocrosslinking agent, and 10-30 parts of Zr-MOPs / ZrO2 dispersion are mixed and stirred evenly to obtain the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide; The thermosetting agent is selected from one or more of the following diisocyanates: toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, and isophorone diisocyanate curing agents; The photoinitiator is selected from one or more of 2,4,6-trimethylbenzoyl, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and bibenzoyl, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone; The photocrosslinking agent is selected from one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and hexanediol diacrylate.

10. A high refractive index adhesive film, characterized in that, It is prepared by the following method: the high refractive index adhesive based on aminozirconium-based metal-organic polyhedral dispersed zirconium dioxide as described in any one of claims 1-8 is uniformly coated on a heavy release film, baked at 100-150℃ for 1.5-6 min to obtain an adhesive layer with a thickness of 25-100 μm, a light release film is attached to the adhesive surface, and cured to obtain the high refractive index adhesive film.

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