Packaging composition, packaging barrier film and semiconductor device

Abstract

The invention relates to a packaging composition which is characterized in that the packaging composition comprises nitrogen-containing heterocyclic acrylate, a photocuring monomer and a photoinitiator, the structural general formula of the nitrogen-containing heterocyclic acrylate is as shown in formula (1): (1) wherein X is a substituent group with 6-30 carbon atoms, an aromatic substituent group without heteroatoms, or a substituent group containing nitrogen, sulfur or oxygen atoms; according to the nitrogen-containing heterocyclic acrylate monomer, nitrogen atoms of a pyridine ring serve as main capture sites of water molecules and metal ions, substituent groups containing additional heteroatoms (such as O, N and S) are introduced into specific positions of the pyridine ring to construct secondary capture sites, and the synergistic barrier effect of a packaging barrier film on the water molecules and the metal ions is achieved; therefore, the packaging performance of the packaging composition barrier film is remarkably improved, and the service life of a device is prolonged.

Description

Technical Field

[0001] This invention belongs to the field of thin-film encapsulation technology for organic light-emitting devices, specifically relating to an encapsulation composition, an encapsulation barrier film, and a semiconductor device. Background Technology

[0002] With the rapid development of flexible displays, encapsulation technology has become a core factor determining product lifespan and reliability. If the encapsulation material cannot effectively prevent moisture and oxygen from entering these display devices, the luminescent materials used in these devices are easily corroded by water and oxygen, resulting in various side reactions that cause material degeneration, loss of their original function, and ultimately, malfunction of the display device. Therefore, it is necessary to use encapsulation materials to completely isolate the electronic devices from the outside air. Thin-film encapsulation (TFE) technology uses inkjet printing to precisely spray liquid encapsulation material onto an inorganic thin-film barrier layer on the device surface to achieve barrier properties; some layers are only micrometers thick. Thin-film encapsulation technology is currently the preferred solution for flexible display devices. Using this method, it can effectively prevent the intrusion of moisture and oxygen, while reducing the overall stress of the TFE film layer and minimizing bending cracks.

[0003] Currently, acrylate compounds are the mainstream materials in the field of thin-film encapsulation for display devices, favored for their high curing efficiency, excellent thermal stability, and good mechanical properties. However, the acrylate monomers widely used in current technologies are mainly based on benzene rings and aliphatic chains, which inherently limits the material's ability to provide deep protection against water vapor and metal ions. Specifically, these traditional structures lack effective functional sites, making it difficult to actively address the two core causes of encapsulation failure: 1) Metal ion migration: Metal ions (such as Na⁺ and Ca²⁺) remaining during device fabrication or invading from the outside migrate to the light-emitting functional layer under the drive of an electric field or concentration gradient, leading to luminescence quenching and device performance degradation. Existing benzene ring or ester group structures exhibit a "passive defense" characteristic against such ions, with limited blocking effect. 2) Water molecule penetration: Once trace amounts of water molecules in the environment penetrate into the device, they will directly lead to irreversible oxidation and failure of organic light-emitting materials and electrodes. Traditional acrylate resins can only provide physical barriers to water molecules and cannot fundamentally "remove" the already penetrated trace amounts of water vapor.

[0004] Therefore, there is an urgent need to design and develop acrylate compounds based on nitrogen-containing heterocyclic compounds to achieve high-performance packaging of flexible display devices. Summary of the Invention

[0005] The purpose of this invention is to overcome the limitations of existing nitrogen-containing heterocyclic designs and to creatively propose a nitrogen-containing heterocyclic acrylate monomer that has a synergistic effect on the capture of water molecules and metal ions, thereby significantly improving the encapsulation performance of the composition and the service life of the device.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] In a first aspect, this application provides an encapsulation composition comprising a nitrogen-containing heterocyclic acrylate, a photocurable monomer, and a photoinitiator, wherein the nitrogen-containing heterocyclic acrylate has the general structural formula shown in formula (1):

[0008] (1)

[0009] Wherein, X is a substituent with 6 to 30 carbon atoms, including aromatic substituents without heteroatoms, or substituents containing nitrogen, sulfur or oxygen atoms.

[0010] In some possible implementations, the heteroatom-free aromatic substituent includes at least one of phenyl, naphthyl, anthraceneyl, phenanthryl, and fluorenyl.

[0011] In some possible implementations, the nitrogen-containing substituents include at least one of the following structures: .

[0012] In some possible implementations, the substituents containing the sulfur atom include at least one of the following structures: .

[0013] In some possible implementations, the substituents of the oxygen-containing atom include at least one of the following structures: .

[0014] In some possible implementations, the photocurable monomer is selected from C1 to C2. 30 Monofunctional (meth)acrylates of monohydric alcohols, C2 to C3 30 di(meth)acrylates of diols, triols, tetraols or pentaols, C3 to C4 30 At least one of the tri(meth)acrylates of triols, tetraols or pentaols.

[0015] In some possible embodiments, the photoinitiator is selected from at least one of bisbenzoylphenylphosphine oxide, hydroxybenzophenone, benzoyl acrylate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, or benzoyldiphenylphosphine oxide.

[0016] In some possible embodiments, the nitrogen-containing heterocyclic acrylate content is 10-50 wt%, the photocurable monomer content is 10-85 wt%, and the photoinitiator content is 0.5-5 wt%.

[0017] Secondly, this application provides an encapsulation barrier film, which is formed by curing the encapsulation composition provided in the first aspect of this application.

[0018] Thirdly, this application provides a semiconductor device that includes the encapsulation barrier film provided in the second aspect of this application.

[0019] Beneficial effects:

[0020] 1. A nitrogen-containing heterocyclic acrylate with synergistic effect on the capture of water molecules and metal ions is proposed: the nitrogen atom of the pyridine ring is used as the main site for metal ion capture. At the same time, secondary capture sites are constructed by introducing substituents containing additional heteroatoms (such as O, N, S) at specific positions of the pyridine ring, thereby achieving a synergistic barrier effect on water molecules and metal ions, thus significantly improving the encapsulation performance and device life of the barrier film of the encapsulation composition. Detailed Implementation

[0021] The embodiments of the present invention will be described in detail below with reference to the examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and not to limit the scope of the invention. Specific conditions not specified in the examples shall be carried out under conventional conditions or the manufacturer's recommended conditions. If the manufacturers of the reagents or instruments used are not specified, they can be conventional products that are commercially available or purchased.

[0022] It should be noted that the following embodiments are examples of this application and are used only to illustrate this application, and are not intended to limit this application. Other combinations and various modifications within the scope of this application are possible without departing from the spirit or scope of this application.

[0023] The encapsulation composition, encapsulation barrier film, and semiconductor device provided in this application are described in detail below.

[0024] <Encapsulation Composition>

[0025] This embodiment provides an encapsulation composition comprising a nitrogen-containing heterocyclic acrylate, a photocurable monomer, and a photoinitiator.

[0026] Nitrogen-containing heterocyclic acrylates

[0027] In this embodiment, the general formula of the nitrogen-containing heterocyclic acrylate structure is shown in formula (1):

[0028] (1)

[0029] Wherein, X is a substituent with 6 to 30 carbon atoms, including aromatic substituents without heteroatoms, or substituents containing nitrogen, sulfur or oxygen atoms.

[0030] In this embodiment, a nitrogen-containing pyridine ring is introduced onto the acrylate. The lone pair electrons of the nitrogen atom on the pyridine ring can act as a Lewis base, actively capturing metal ions through coordination. Simultaneously, this nitrogen atom can also act as a hydrogen bond acceptor, anchoring water molecules and inhibiting water molecule diffusion to some extent.

[0031] However, the inventors discovered that the trapping sites and capabilities of a single nitrogen atom are limited, and its electron cloud density and spatial configuration are not optimized, making it difficult to achieve the best synergistic trapping effect for both metal ions and water molecules simultaneously.

[0032] In this embodiment, substituents with 6 to 30 carbon atoms are further introduced onto the pyridine ring, including aromatic substituents without heteroatoms, or substituents containing nitrogen, sulfur, or oxygen atoms.

[0033] Among them, aromatic substituents without heteroatoms, and aromatic substituents with a large number of conjugated structures, can increase the electron cloud density of the nitrogen atom in the pyridine ring, thereby improving its ability to capture metal ions or water molecules and effectively suppressing the migration of metal ions and the permeation of water molecules in the encapsulation barrier membrane. Examples of aromatic substituents without heteroatoms include: phenyl, naphthyl, anthraceneyl, phenanthryl, fluorene, and other polycyclic aromatic hydrocarbons.

[0034] Among them, the nitrogen atom in the nitrogen-containing substituent can further provide a site for capturing metal ions or water molecules. The conjugated structure formed with other aromatic rings can also improve its ability to capture metal ions or water molecules, effectively suppressing the migration of metal ions and the permeation of water molecules in the encapsulation barrier membrane. For example, the nitrogen-containing substituent is shown in formula (2).

[0035]

[0036] Equation (2)

[0037] Among them, the sulfur atoms in the substituents containing sulfur atoms also have lone pairs of electrons or form strongly polar groups such as sulfone groups, which can further provide sites for capturing metal ions or water molecules. The conjugated structure formed with other aromatic rings can also improve its ability to capture metal ions or water molecules, effectively suppressing the migration of metal ions and the permeation of water molecules in the encapsulation barrier membrane. For example, the substituents containing sulfur atoms are shown in formula (3).

[0038]

[0039] Equation (3)

[0040] Among them, the oxygen atoms in the oxygen-containing substituents also have lone pairs of electrons, which can further provide sites for capturing metal ions or water molecules. The conjugated structure formed with other aromatic rings can also improve its ability to capture metal ions or water molecules, effectively suppressing the migration of metal ions and the permeation of water molecules in the encapsulation barrier membrane. For example, the oxygen-containing substituents are shown in formula (4).

[0041]

[0042] Equation (4)

[0043] This embodiment also provides a method for preparing the above-mentioned nitrogen-containing heterocyclic acrylate, wherein the method for preparing nitrogen-containing heterocyclic acrylate containing aromatic substituents without heteroatoms is as follows:

[0044]

[0045] Under a nitrogen atmosphere, 5-bromo-2-iodopyridine and arylboronic acid were heated to react in the presence of Pd(PPh3)4 and an aqueous solution of sodium carbonate. After extraction, drying, and purification, the reaction solution yielded intermediate 1, an arylpyridine brominated precursor. Ethylene glycol was added to intermediate 1, and the mixture was heated to react in the presence of potassium carbonate and cuprous iodide. After washing with water, extraction, drying, and purification, intermediate 2 was obtained. Intermediate 2 was then dissolved in triethylamine with methacryloyl chloride and reacted at room temperature. The reaction solution was purified by silica gel column chromatography to obtain a nitrogen-containing heterocyclic acrylate containing aromatic substituents without heteroatoms.

[0046] The preparation method of nitrogen-containing heterocyclic acrylates containing nitrogen, sulfur, or oxygen atom substituents is similar to that of nitrogen-containing heterocyclic acrylates containing aromatic substituents without heteroatoms, with only slight differences in raw materials: nitrogen-containing heterocyclic acrylates containing nitrogen, sulfur, or oxygen atom substituents are prepared by reacting iodine-substituted nitrogen, sulfur, or oxygen atoms with 5-bromo-2-(tributyltin)pyridine, and the brominated precursor is synthesized under the catalysis of Pd(PPh3)4. The subsequent reaction steps and purification methods are consistent with the preparation method of nitrogen-containing heterocyclic acrylates containing aromatic substituents without heteroatoms, and will not be described in detail in this embodiment.

[0047] Photocurable monomers

[0048] In this embodiment, the photocurable monomer is at least one of the following: C1 to C1. 30 Monofunctional (meth)acrylates of monohydric alcohols; C2 to C 30 di(meth)acrylates of diols, triols, tetraols or pentaols, C3 to C4 30The tri(meth)acrylate of triols, tetraols or pentaols, wherein the monomers may include acrylate monomers containing monohydric or polyhydric alcohols, such materials have high curing rate, light transmittance and low viscosity at room temperature, and can effectively adjust the viscosity, tension and curing rate of the encapsulated components.

[0049] Photoinitiator

[0050] In this embodiment, the photoinitiator comprises any typical photopolymerization initiator capable of performing photocuring reactions, specifically one or more of the following: bisbenzoylphenylphosphine oxide, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, or benzoyldiphenylphosphine oxide. Preferably, phosphorus initiators are commonly used, as they have good solubility with monomers, absorption wavelengths up to 430 nm, are suitable for colored UV curing systems, and are colorless after decomposition, exhibiting excellent resistance to yellowing.

[0051] This embodiment also provides a method for preparing the above-mentioned encapsulation composition, as follows: 10-50 wt% of nitrogen-containing heterocyclic acrylate, 10-85 wt% of photocurable monomer and 0.5-5 wt% of photoinitiator are placed in a container according to the mass fraction, and mixed and stirred at room temperature until each component is dissolved to form a homogeneous encapsulation composition.

[0052] <Encapsulation barrier film>

[0053] The encapsulation composition provided in this embodiment is used to form a coating sample by inkjet printing, and then cured by ultraviolet light to form a photocurable encapsulation barrier film. The specific steps are as follows:

[0054] S1. The above-mentioned encapsulation composition is coated on the surface of the electronic device to be encapsulated to form an organic layer;

[0055] S2. Irradiate the organic layer with ultraviolet light with a wavelength of 280–450 nm for 20–300 s to solidify it into an organic thin film with a thickness of 5–40 μm to protect electronic devices.

[0056] Semiconductor Devices

[0057] This embodiment also relates to the application of semiconductor devices including the above-described encapsulation barrier film in fields such as organic electroluminescent devices or organic photovoltaic devices.

[0058] Example

[0059] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that the embodiments are merely illustrative of the present invention and should not be construed as specific limitations thereof.

[0060] In this embodiment, the raw materials are all commercially available bulk industrial products, and the manufacturers include BASF, Wanhua Chemical, Asahikawa Chemical, Huafeng, etc.

[0061] Preparation Example 1

[0062] Nitrogen heterocyclic acrylates 1

[0063]

[0064] Under a nitrogen atmosphere, 283.9 g of 5-bromo-2-iodopyridine, 189.2 g of 1-naphthoronic acid, and 57.8 g of Pd(PPh3)4 were added to a mixed solvent of toluene and 2.0 mol / L sodium carbonate aqueous solution (1550 mL, volume ratio 1:1). The mixture was heated to 90 °C and stirred for 20 hours. The reaction solution was extracted three times with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain the filtrate. The solvent was removed by rotary evaporation. The crude product was adsorbed onto silica gel and purified by column chromatography. The eluent was a mixture of petroleum ether and dichloromethane. The final product was the brominated precursor 5-bromo-2-naphthylpyridine. Under a nitrogen atmosphere, 142.1 g of 5-bromo-2-naphthylpyridine, 400 g of ethylene glycol, 13.8 g of potassium carbonate, and 2.0 g of cuprous iodide were added to a reaction flask. The mixture was heated to 130 °C and stirred for 24 h. The reaction mixture was then cooled to room temperature, washed with water, and extracted with dichloromethane to obtain an organic layer. The organic layer was dried with anhydrous sodium sulfate and concentrated to remove dichloromethane. The residue was purified by silica gel column chromatography to obtain 107.4 g of 2-[(6-naphthyl-3-pyridyl)oxy]ethanol. The obtained 2-[(6-naphthyl-3-pyridyl)oxy]ethanol was then dissolved in 500 mL of triethylamine with 50.8 g of methacryloyl chloride. The mixture was stirred at room temperature under a nitrogen atmosphere for 24 h and then concentrated. The residue was purified by silica gel column chromatography to obtain 112.9 g of 2-[(6-naphthyl-3-pyridyl)oxy]ethyl methacrylate, with a yield of 64%.

[0065] Preparation Example 2

[0066] Nitrogen heterocyclic acrylates 2

[0067]

[0068] Under a nitrogen atmosphere, 114 g of 2-bromocarbazole, 228 g of 5-bromo-2-(tributyltin)pyridine, and 26 g of Pd(PPh3)4 were added to toluene (2500 mL). The mixture was heated to 120 °C and stirred for 24 hours. After cooling, the solvent was removed by rotary evaporation. The crude product was adsorbed onto silica gel and purified by column chromatography. The eluent was a mixture of petroleum ether and dichloromethane (volume ratio = 1:3). The final product was the brominated precursor 5-bromo-2-carbazole pyridine. Under a nitrogen atmosphere, 161.6 g of 5-bromo-2-carbazole pyridine, 400 g of ethylene glycol, 13.8 g of potassium carbonate, and 2.0 g of cuprous iodide were added to a reaction flask. The mixture was heated to 130 °C and stirred for 24 h. The reaction mixture was then cooled to room temperature, washed with water, and extracted with dichloromethane to obtain the organic layer. The organic layer was dried with anhydrous sodium sulfate and concentrated to remove dichloromethane. The residue was purified by silica gel column chromatography. 110.5 g of 2-[(6-carbazole-3-pyridinyl)oxy]ethanol was then dissolved with 45.5 g of methacryloyl chloride in 500 mL of triethylamine. The mixture was stirred at room temperature under a nitrogen atmosphere for 24 h and then concentrated. The residue was purified by silica gel column chromatography to obtain 90.6 g of 2-[(6-carbazole-3-pyridinyl)oxy]ethyl methacrylate, with a yield of 67%.

[0069] Preparation Example 3

[0070] Nitrogen heterocyclic acrylates 3

[0071]

[0072] Under a nitrogen atmosphere, 160 g of 4-iodo-diphenyl sulfone, 228 g of 5-bromo-2-(tributyltin)pyridine, and 26 g of Pd(PPh3)4 were added to toluene (2500 mL). The mixture was heated to 120 °C and stirred for 24 hours. After cooling, the solvent was removed by rotary evaporation. The crude product was adsorbed onto silica gel and purified by column chromatography. The eluent was a mixture of petroleum ether and dichloromethane (volume ratio = 1:3), finally yielding the brominated precursor 5-bromo-2-diphenyl sulfone pyridine. Under a nitrogen atmosphere, 187.1 g of 5-bromo-2-diphenyl sulfone pyridine, 400 g of ethylene glycol, 13.8 g of potassium carbonate, and 2.0 g of cuprous iodide were added to a reaction flask. The mixture was heated to 130 °C and stirred for 24 h. The reaction mixture was then cooled to room temperature, washed with water, and extracted with dichloromethane to obtain the organic layer. The organic layer was dried with anhydrous sodium sulfate and then concentrated to remove dichloromethane. The residue was purified by silica gel column chromatography to obtain 151.2 g of 2-[(6-diphenylsulfonyl-3-pyridinyl)oxy]ethanol. The obtained 2-[(6-diphenylsulfonyl-3-pyridinyl)oxy]ethanol was then dissolved in 500 mL of triethylamine with 53.7 g of methacryloyl chloride. The mixture was stirred at room temperature for 24 h under a nitrogen atmosphere and then concentrated. The residue was purified by silica gel column chromatography to obtain 141.4 g of ethyl 2-[(6-diphenylsulfonyl-3-pyridinyl)oxy]methacrylate, with a yield of 67%.

[0073] Preparation Example 4

[0074] Nitrogen heterocyclic acrylates 4

[0075]

[0076] Under a nitrogen atmosphere, 134 g of 2-bromo-benzofuran, 228 g of 5-bromo-2-(tributyltin)pyridine, and 26 g of Pd(PPh3)4 were added to toluene (2500 mL). The mixture was heated to 120 °C and stirred for 24 hours. After cooling, the solvent was removed by rotary evaporation. The crude product was adsorbed onto silica gel and purified by column chromatography. The eluent was a mixture of petroleum ether and dichloromethane (volume ratio = 1:3), finally yielding the brominated precursor 5-bromo-2-benzofuran pyridine. Under a nitrogen atmosphere, 155.2 g of 5-bromo-2-benzofuran pyridine, 400 g of ethylene glycol, 13.8 g of potassium carbonate, and 2.0 g of cuprous iodide were added to a reaction flask. The mixture was heated to 130 °C and stirred for 24 h. The reaction mixture was then cooled to room temperature, washed with water, and extracted with dichloromethane to obtain the organic layer. The organic layer was dried with anhydrous sodium sulfate and then concentrated to remove dichloromethane. The residue was purified by silica gel column chromatography to obtain 123.1 g of 2-[(6-benzofuran-3-pyridinyl)oxy]ethanol. The obtained 2-[(6-benzofuran-3-pyridinyl)oxy]ethanol was then dissolved in 500 mL of triethylamine with 53.7 g of methacryloyl chloride. The mixture was stirred at room temperature for 24 h under a nitrogen atmosphere and then concentrated. The residue was purified by silica gel column chromatography to obtain 87.3 g of ethyl 2-[(6-benzofuran-3-pyridinyl)oxy]methacrylate, with a yield of 65%.

[0077] Example 1

[0078] 1.1 g of 2-[(6-naphthyl-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 1,6-hexanediol dimethacrylate and 0.1 g of bisbenzoylphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 1.

[0079] Example 2

[0080] 1.1 g of 2-[(6-carbazole-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 1,6-hexanediol dimethacrylate and 0.1 g of bisbenzoylphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 2.

[0081] Example 3

[0082] 1.1 g of 2-[(6-diphenylsulfonyl-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 1,6-hexanediol dimethacrylate and 0.1 g of bisbenzoylphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 3.

[0083] Example 4

[0084] 1.1 g of 2-[(6-benzofuran-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 1,6-hexanediol dimethacrylate and 0.1 g of bisbenzoylphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 4.

[0085] Example 5

[0086] 1.1 g of 2-[(6-carbazole-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 2-phenylethyl (meth)acrylate and 0.1 g of bisbenzoylphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 5.

[0087] Example 6

[0088] 1.1 g of 2-[(6-carbazole-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 1,6-hexanediol dimethacrylate and 0.1 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 6.

[0089] Example 7

[0090] 0.1 g of 2-[(6-carbazole-3-pyridyl)oxy]ethyl methacrylate, 3.0 g of 2,6-hexanediol dimethacrylate and 0.1 g of bisbenzoylphenylphosphine oxide were stirred at room temperature in the dark for 3 h to obtain encapsulation composition 7.

[0091] Comparative Example 1

[0092] In Example 1, 2-[(6-naphthyl-3-pyridyl)oxy]ethyl methacrylate was replaced with 2-[(3-pyridyl)oxy]ethyl methacrylate, while all other aspects remained the same.

[0093] Comparative Example 2

[0094] In Example 1, 2-[(6-naphthyl-3-pyridyl)oxy]ethyl methacrylate was replaced with 2-(methoxy)ethyl methacrylate, while all other aspects remained the same.

[0095] Evaluation of light curing rate

[0096] The encapsulation composition was used to form a coating sample via inkjet printing, followed by exposure to 10 mW / cm². 2The film was cured by irradiation with a UV lamp for 200 s, forming a 26 μm thick encapsulation barrier film. The characteristic absorption peak intensities at approximately 1635 cm⁻¹ (C=C double bond stretching vibration) and approximately 1720 cm⁻¹ (C=O carbonyl stretching vibration) were measured using a Fourier transform infrared spectroscopy (FT-IR, Nicoleti S50, Thermo Fisher Scientific Inc.). The photocuring rate was calculated using the following formula: Photocurability = [1 - (F / S)] * 100; where F is the ratio of the absorption peak intensity near 1635 cm⁻¹ to the absorption peak intensity near 1720 cm⁻¹; and S is the ratio of the absorption peak intensity near 1635 cm⁻¹ to the absorption peak intensity near 1720 cm⁻¹.

[0097] Light transmittance evaluation

[0098] The transmittance of the obtained photocurable film in the visible light range of 400 nm to 800 nm was measured using a UV-Vis spectrophotometer.

[0099] Yellowness Index Evaluation

[0100] Using a spectrophotometer equipped with a standard D65 light source, the tristimulus values ​​X, Y, and Z of the photocurable film in the CIE XYZ colorimetric system were measured in transmission mode according to ASTM E313 standard. The yellowness index (YI) was calculated using the following formula: YI = 100 * (Cx*X – Cz*Z) / Y.

[0101] Water vapor transmission rate evaluation

[0102] The encapsulation composition was printed into a film using inkjet printing. After peeling off the film, the water vapor transmission rate was tested on a permeability meter. The film area was 4 inches in diameter, larger than the permeation chamber area. The test was conducted at 38°C and 90%RH in a circulating mode, and the water vapor transmission rate was recorded (unit: g / m³). 2 *24h).

[0103] Evaluation of the maximum adsorption capacity of metal ions

[0104] Accurately weighed solidified encapsulation barrier film fragments were immersed in a known concentration of 100 ppm CuCl2 solution. After 24 hours, adsorption equilibrium was reached. The supernatant was collected, and the remaining Cu was measured using ICP-MS. 2+ Ion concentration, calculated by the concentration difference, is the amount of adsorption per unit mass of the thin film (unit: mg Cu). 2+ / g film).

[0105] The performance evaluation results of the examples and comparative examples are shown in Table 1.

[0106] Table 1

[0107] UV curing rate (%) Light transmittance (%) Yellowness Index <![CDATA[Water vapor transmission rate (g / m 2 *24h)]]> <![CDATA[Maximum adsorption capacity of metal ions (mg Cu 2+ / g)]]> Example 1 96.4 98.1 2.86 1.62 13.2 Example 2 97.7 99.7 2.23 1.12 20.6 Example 3 96.7 99.6 2.51 1.21 18.5 Example 4 97.4 99.3 2.46 1.25 17.4 Example 5 97.5 99.4 2.31 1.18 19.4 Example 6 72.5 74.3 3.26 11.67 2.17 Example 7 94.1 95.2 2.91 6.23 1.04 Comparative Example 1 91.2 92.4 6.54 8.43 2.3 Comparative Example 2 82.6 77.3 8.42 16.59 0.2

[0108] The above test results demonstrate that the nitrogen-containing heterocyclic acrylate, based on the unique synergistic design of the pyridine ring and multifunctional substituents of this invention, successfully combines excellent barrier properties with superior overall performance in its UV-curable encapsulation barrier film, as specifically shown below:

[0109] 1. Outstanding curing performance and film-forming properties: This composition exhibits a high photocuring rate, ensuring the efficiency of the encapsulation process; the film formed after curing is dense and uniform, providing an ideal structural basis for achieving high-efficiency barrier properties.

[0110] 2. Superior optical performance: While achieving efficient barrier properties, this optical film maintains extremely high transmittance and extremely low yellowness index, fully meeting the stringent requirements of high-end display devices for the optical transparency of packaging materials.

[0111] 3. Enhanced Water Vapor Barrier and Metal Ion Adsorption Performance: The encapsulation barrier film exhibits low water vapor permeability and high metal ion adsorption capacity, directly confirming the "active capture" mechanism of this invention. The pyridine nitrogen atoms and synergistic sites on the substituents in the nitrogen-containing heterocyclic acrylate effectively anchor and lock water molecules penetrating the film, significantly delaying the permeation and diffusion of water vapor into the device. Furthermore, a comparison of water vapor permeability data between the examples and comparative examples further demonstrates that the substituent-containing nitrogen-containing heterocyclic acrylate monomer has a synergistic and promoting effect on the barrier effect of water molecules and metal ions compared to the pyridine group alone.

[0112] It should be noted that, based on the explanations and descriptions in the foregoing specification, those skilled in the art can make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and alterations to the present invention should also be within the scope of protection of the claims of the present invention. Furthermore, although some specific terms are used in this specification, these terms are only for convenience of explanation and do not constitute any limitation on the invention.

Claims

1. An encapsulant composition characterized in that, Photocurable composition comprising nitrogen-containing heterocyclic acrylate Monomer and photoinitiator, the nitrogen-containing heterocyclic acrylate structure general formula as shown in formula (1): （1） Wherein, X is a substituted group of carbon atoms 3~30, including aromatic substituent group without heteroatom, or containing nitrogen, sulfur or oxygen atom.

2. The encapsulant composition of claim 1, wherein The aromatic substituent group without heteroatom includes at least one of phenyl, naphthyl, anthryl, phenanthryl, fluorenyl.

3. The encapsulant composition of claim 1, wherein The nitrogen atom containing substituent group includes at least one of the following structures: 。 4. The encapsulant composition of claim 1, wherein The sulfur atom containing substituent group includes at least one of the following structures: 。 5. The encapsulant composition of claim 1, wherein The oxygen atom containing substituent group includes at least one of the following structures: 。 6. The encapsulant composition of claim 1, wherein said photo-curable monomers are selected from at least one of mono-functional (meth)acrylates of mono-ols, C2 to C 30 diols, triols, tetraols or pentaols, di(meth)acrylates of diols, triols, tetraols or pentaols, C3 to C 30 triols, tetraols or pentaols, tri(meth)acrylates of triols, tetraols or pentaols. 30 triols, tetraols or pentaols, tri(meth)acrylates of triols, tetraols or pentaols.

7. The encapsulant composition of claim 1, wherein The photoinitiator is selected from at least one of the following: benzoin phenyl phosphine oxide, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino) benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone or benzoyl diphenyl phosphine oxide.

8. The encapsulant composition of claim 1, wherein The nitrogen-containing heterocyclic acrylate content is 10~50wt%, the photocurable monomer content is 10~85 wt%, and the photoinitiator content is 0.5~5wt%.

9. A package barrier film characterized by, Cured from the packaging composition of any one of claims 1~8.

10. A semiconductor device, characterized by comprising: The packaging barrier film comprising the packaging composition of claim 9.

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