A compound for encapsulating a thin film, a composition comprising the same, and a method of preparing an encapsulating thin film

Abstract

The application discloses a compound for packaging film, a composition containing the same and a preparation method of the packaging film, and relates to the technical field of film packaging. The compound for packaging film has the structure shown in the formula I; the application of the compound for packaging film can reduce the water vapor and gas permeability, prolong the service life of a display device, and the packaging film has high light transmittance, low permittivity and low shrinkage stress after curing, so that no any deviation can be generated.

Description

Technical Field

[0001] This invention relates to the field of thin film encapsulation technology, and more specifically to a compound for encapsulating thin films, a composition comprising the same, and a method for preparing the encapsulated thin film. Background Technology

[0002] With the rapid development of electronic information technology, electronic information products are moving towards high frequency, high speed, multifunctionality, and miniaturization, ultra-thinness, and lightweight design. Simultaneously, the development of very large-scale integrated circuits (VLSI) has led to a continuous increase in interconnect density within chips, while the width and spacing of interconnect lines are decreasing. This results in increasingly pronounced parasitic effects caused by interconnect resistance (R) and capacitance (C), leading to severe signal delays. Using low-dielectric-constant packaging materials that are less affected by transmitted signals is a primary approach to addressing this problem. Therefore, there is an urgent need for low-dielectric-constant (k<3) materials with good performance. Compared to traditional low-dielectric inorganic materials (such as SiO2), low-dielectric organic materials have attracted significant interest from researchers due to their advantages such as diverse molecular design and good processing performance.

[0003] Fluorine-containing functional groups are a new type of specialty polymer materials with excellent low dielectric properties, and they are widely used in aerospace, mechanical and electronic engineering, automotive manufacturing, chemical and petroleum industries, medical and health fields, and many other areas. Therefore, developing novel fluorine-containing functional group polymer materials with low dielectric constants is of great significance. Summary of the Invention

[0004] In view of this, the present invention provides a compound for encapsulating films, a composition comprising the same, and a method for preparing the encapsulating film, which can reduce the transmittance of water vapor and gas, extend the service life of the display device, and the encapsulating film has high light transmittance, low valence electrical constant, and low shrinkage stress after curing, thereby achieving no displacement.

[0005] To achieve the above objectives, the present invention first provides a compound for encapsulating thin films, the structure of which is shown in Formula I:

[0006] ; Wherein, R1 and R2 are monosubstituted or polysubstituted; R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C20 alkyl, substituted or unsubstituted C6~C30 aryl, fluoro, and trifluoromethyl. R3 is monosubstituted or polysubstituted; selected from hydrogen, fluorine, trifluoromethyl, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C18 aryl; R4 and R5 are selected from hydrogen, substituted or unsubstituted methyl, and fluorine groups; R6 is selected from methyl or ethyl; X1 is selected from C3~C20 alkyl chains or C1~C20 alkoxy chains; L1 is selected from hydrogen, substituted or unsubstituted C1-20 alkyl groups, and substituted or unsubstituted C1-20 alkoxy groups.

[0007] Preferably, the substitution or non-substitution refers to substitution by one, two or more substituents selected from the following: fluoro, trifluoromethyl, C1-C6 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, C3-C24 heterocyclic, or substitution by two or more substituents linked together from the substituents shown above, or propenyl derivatives.

[0008] Preferably, the compound used for encapsulating the film is selected from one of the following chemical formulas: .

[0009] The present invention also provides a photocurable composition for encapsulation, the composition comprising the following raw materials in weight percentages: component A 9.5~90%, component B 9.5~90%, component C 0.5~10%; Component A is the aforementioned compound used for encapsulating films; Component B is any one or a combination of several of the following: monofunctional methacrylates of C1-C30 monohydric or polyhydric alcohols that can be cured by light; difunctional methacrylates of C2-C30 monohydric or polyhydric alcohols that can be cured by light; and polyfunctional methacrylates of C3-C30 monohydric or polyhydric alcohols that can be cured by light. Component C is a photocrosslinking initiator.

[0010] Preferably, the photocurable C1-C30 monohydric or polyhydric monohydric alcohol monofunctional methacrylate is any one or a combination of several of lauryl acrylate, ethoxyethyl acrylate, butyl acrylate, hydroxyethyl acrylate, isobornyl acrylate, tetrahydrofuran acrylate, methacrylate phosphate, and isobornyl methacrylate. The photocurable C2-C30 monohydric or polyhydric difunctional methacrylate is any one or a combination of several of the following: diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, propoxy neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, 20(ethoxy)bisphenol A diacrylate, and glycerol diacrylate. The photocurable C3-C30 monohydric or polyhydric alcohol polyfunctional methacrylate is any one or a combination of several of the following: trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane triol triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tripropylene acrylate, propoxylated pentaerythritol propylene acrylate, di(trimethylolpropane)tetraacrylate, triethylene glycol dimethacrylate, long-chain aliphatic hydrocarbon glycidyl ether acrylate, dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, phthalic acid diethanolate diacrylate, ethoxylated trimethylolpropane triol triacrylate, propoxylated trimethylolpropane triol triacrylate, propoxylated glycerol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, and ethoxylated neopentyl glycol methoxy monoacrylate. The photocrosslinking initiator is any one or a combination of several of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine ester.

[0011] The present invention also provides a method for preparing the above-mentioned photocurable composition for encapsulation, comprising the following steps: (1) Weigh each raw material according to the weight percentage of the photocurable composition for encapsulation, and set aside; (2) After mixing components A, B and C, the mixture is stirred under vacuum and filtered to obtain the photocurable composition for encapsulation.

[0012] The vacuum stirring temperature is 50℃ and the time is 80h.

[0013] The present invention also provides an encapsulation film, which is formed by laminating an inorganic layer and an organic layer 1 to 5 times, with the outermost layer being an inorganic layer; wherein the material of the organic layer is the above-mentioned photocurable composition for encapsulation.

[0014] Preferably, the inorganic layer material is selected from any one or a combination of several of silicon nitride, silicon oxynitride, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and zinc oxide, and has a thickness of 8~12μm.

[0015] The present invention also provides a method for preparing the encapsulation film as described above, comprising the following steps: the inorganic layer is prepared by coating an inorganic layer material onto the surface of the object to be encapsulated by chemical vapor deposition to form an inorganic layer; an organic layer is deposited on the inorganic layer by inkjet printing; and then an organic layer is obtained by UV curing. This process is repeated, with the outermost layer being an inorganic layer, to obtain the encapsulation film.

[0016] As can be seen from the above technical solutions, the present invention discloses a compound for encapsulating films, a composition containing the same, and a method for preparing the encapsulating film. Compared with the prior art, its advantages are as follows: The application of the compound to prepare the encapsulation film can reduce the transmittance of water vapor and gas, thereby extending the service life of the display device. The encapsulation film has high light transmittance, low valence electrical constant, and low shrinkage stress after curing, thus achieving no displacement. Detailed Implementation

[0017] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Example 1 Preparation of G-2

[0019] Step 1: Weigh bis(4-bromophenyl)diphenylsilane (CAS: 18733-91-0, 1 eq), 3,5-difluoro-4-(trimethylsilyl)phenylboronic acid (CAS: 1257792-90-7, 1.01 eq), anhydrous potassium carbonate (3 eq), tetrahydrofuran (10 eq), and water (10 eq) and add them to the reactor. Purge with nitrogen twice. Under a nitrogen atmosphere, add tetra(triphenylphosphine)palladium (symbol: Pd(PPh3)4, 0.03 eq) to the reaction system and react at 75°C for 12 hours until the reaction is complete. Add ethyl acetate (5 eq) to the phase system, stir for 5 minutes, allow to stand, and separate the phases. Extract the aqueous phase twice with ethyl acetate, combine the organic phases, concentrate, and perform column chromatography using petroleum ether and ethyl acetate as eluents to obtain intermediate S1 in 42% yield.

[0020] HPLC: ≥99.3%.

[0021]

[0022] Step 2: Under a nitrogen atmosphere, intermediate S1 (1 eq), ethylene glycol (0.8 eq), anhydrous potassium carbonate (2 eq), and copper acetate (0.05 eq) were added to the reaction flask. The mixture was heated to 130°C and reacted for 24 hours until the reaction was complete. After cooling to room temperature, water (5 eq) and dichloromethane (5 eq) were added to the system. The mixture was stirred for 10 minutes, allowed to stand, and separated. The aqueous phase was extracted twice with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and subjected to column chromatography. Petroleum ether and ethyl acetate were used as eluents. The mixture was then concentrated to obtain intermediate S2 in 56% yield.

[0023] HPLC: ≥99%.

[0024]

[0025] Step 3: Under a nitrogen atmosphere, intermediate S2 (1 eq), methacryloyl chloride (1.5 eq), and pyridine (8.5 eq) were reacted at room temperature for 24 hours. The mixture was then concentrated and subjected to column chromatography with petroleum ether and ethyl acetate as eluents to obtain the target product G-2 in 38.2% yield.

[0026] HPLC: ≥96%.

[0027] Mass spectrometry reading: 648.29.

[0028] Elemental analysis theoretical values: C, 72.19%; H, 5.90%; F, 5.86%; O, 7.40%; Si, 8.66%; Measured values: C, 72.22%; H, 5.92%; F, 5.81%; O, 7.44%; Si, 8.62%.

[0029] The preparation methods of other compounds used for encapsulation films in this invention are basically the same as those in Example 1, and will not be described in detail here.

[0030] Preparation of photocurable compositions for encapsulation (1) Mix 20g of component A (G-2), 70g of component B (trimethylolpropane triacrylate) and 10g of component C (2-hydroxy-2-methyl-1-phenylpropanone) under vacuum at 50°C for 80h until homogeneous.

[0031] (2) Filter with a syringe filter and detect with a particle counter. When the number of particles with a diameter greater than 0.5 μm is no more than 50, the processed photocurable composition for encapsulation is obtained.

[0032] Preparation of encapsulation film (1) Silicon nitride is selected as the inorganic layer material, and the above-mentioned photocurable composition for encapsulation is selected as the organic layer material; (2) Preparation of inorganic layer: The inorganic layer material is coated onto the surface of the object to be encapsulated by CVD to form an inorganic layer with a thickness of 9 μm; (3) Preparation of the organic layer: The organic layer material is sprayed onto the surface of the inorganic layer using an inkjet printer to form the organic layer, using 100mW / cm 2 Each 10-second exposure to ultraviolet light causes the organic layer to harden; (4) The encapsulation film is formed by repeating the process of alternating inorganic and organic layers three times to deposit coating on the surface of the object to be encapsulated. The final encapsulation film consists of inorganic and organic layers deposited on the surface of the object to be encapsulated.

[0033] Example 2 Monomer G-1 was prepared according to the method of Example 1. A photocurable composition for encapsulation was prepared using 20g of component A (G-1), 70g of component B (triethylene glycol dimethacrylate), and 10g of component C (2-hydroxy-2-methyl-1-phenylpropanone), and an encapsulation film was further prepared.

[0034] Example 3 Monomer G-3 was prepared according to the method of Example 1. A photocurable composition for encapsulation was prepared using 20g of component A (G-3), 70g of component B (propoxylated glycerol triacrylate), and 10g of component C (2-hydroxy-2-methyl-1-phenylpropanone), and an encapsulation film was further prepared.

[0035] Example 4 Monomer G-4 was prepared according to the method in Example 1. A photocurable composition for encapsulation was prepared using 20g of component A (G-4), 70g of component B (propoxylated glycerol triacrylate), and 10g of component C (2-hydroxy-2-methyl-1-phenylpropanone), and an encapsulation film was further prepared.

[0036] Example 5 Monomer G-5 was prepared according to the method of Example 1. A photocurable composition for encapsulation was prepared using 20g of component A (G-5), 70g of component B (propoxylated glycerol triacrylate), and 10g of component C (2-hydroxy-2-methyl-1-phenylpropanone), and an encapsulation film was further prepared.

[0037] Example 6 Monomer G-6 was prepared according to the method in Example 1. A photocurable composition for encapsulation was prepared using 20g of component A (G-6), 70g of component B (propoxylated glycerol triacrylate), and 10g of component C (2-hydroxy-2-methyl-1-phenylpropanone), and an encapsulation film was further prepared.

[0038] Example 7 The difference from Example 1 is that 20g of component A's composition monomer G-2 is replaced with 30g, and 70g of component B's trimethylolpropane triacrylate is replaced with 60g.

[0039] Example 8 The difference from Example 2 is that 20g of component A's composition monomer G-1 was replaced with 30g, and 70g of component B's triethylene glycol dimethacrylate was replaced with 60g.

[0040] Example 9 The difference from Example 3 is that 20g of component A's composition monomer G-3 was replaced with 30g, and 70g of component B's propoxylated glycerol triacrylate was replaced with 60g.

[0041] Example 10 The difference from Example 4 is that 20g of component A's composition monomer G-4 was replaced with 30g, and 70g of component B's propoxylated glycerol triacrylate was replaced with 60g.

[0042] Example 11 The difference from Example 5 is that 20g of component A's composition monomer G-5 was replaced with 30g, and 70g of component B's propoxylated glycerol triacrylate was replaced with 60g.

[0043] Example 12 The difference from Example 6 is that 20g of component A's composition monomer G-6 was replaced with 30g, and 70g of component B's propoxylated glycerol triacrylate was replaced with 60g.

[0044] Comparative Example 1 The compound structure of component A is as follows:

[0045] The preparation methods of the photocurable composition for encapsulation and the encapsulation film are the same as in Example 1.

[0046] Performance testing experiment Water vapor transmission rate was tested on the encapsulation films of Examples 1-12 and Comparative Example 1. The testing instrument was a high-precision water vapor transmission rate tester, model AQUARAN2, manufactured by MOCON Corporation, USA. Testing conditions: Temperature 85℃, relative humidity 85%; Testing duration: 24 hours; The dielectric constant was measured using an HP4194A dielectric spectrum analyzer; the water contact angle was measured using a DSA25 fully automatic video contact angle measuring instrument from Krüss GmbH, Germany, and the average value of three parallel tests was taken; the tensile modulus was tested according to GB / T1040-92.

[0047] The experimental results are shown in Table 1 below:

[0048] The water vapor transmission rate of the encapsulation films in Examples 1-12 and Comparative Example 1 was tested. The difference between Examples 1-12 and Comparative Example 1 is that Component A created in this invention was added in Examples 1-12. The comparison shows that the water vapor transmission rate of the encapsulation film after adding Component A created in this invention is significantly lower than that of the encapsulation film without Component A created in this invention, and the dielectric constant is also reduced. By encapsulating organic light-emitting devices with the above encapsulation films, water vapor can be effectively isolated, and the service life of organic light-emitting devices can be extended.

[0049] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. For the apparatus disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the description is relatively simple; relevant parts can be referred to the method section.

[0050] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A compound for encapsulating thin films, characterized in that, The compound structure used for encapsulating the thin film is shown in Formula I: ； Wherein, R1 and R2 are monosubstituted or polysubstituted; R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C20 alkyl, substituted or unsubstituted C6~C30 aryl, fluoro, and trifluoromethyl. R3 is monosubstituted or polysubstituted; selected from hydrogen, fluorine, trifluoromethyl, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C18 aryl; R4 and R5 are selected from hydrogen, substituted or unsubstituted methyl, and fluorine groups; R6 is selected from methyl or ethyl; X1 is selected from C3~C20 alkyl chains or C1~C20 alkoxy chains; L1 is selected from hydrogen, substituted or unsubstituted C1-20 alkyl groups, and substituted or unsubstituted C1-20 alkoxy groups.

2. The compound for encapsulating thin films according to claim 1, characterized in that, The substitution or non-substitution refers to substitution by one, two or more substituents selected from the following: fluoro, trifluoromethyl, C1-C6 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, C3-C24 heterocyclic, or substitution by two or more substituents linked together from the substituents shown above, or propenyl derivatives.

3. The compound for encapsulating thin films according to claim 1, characterized in that, The compound used for encapsulating the film is selected from one of the following chemical formulas: 。 4. A photocurable composition for encapsulation, characterized in that, The composition comprises the following raw materials in weight percentages: component A 9.5-90%, component B 9.5-90%, component C 0.5-10%; Component A is the compound for encapsulating films as described in claim 1; Component B is any one or a combination of several of the following: monofunctional methacrylates of C1-C30 monohydric or polyhydric alcohols that can be cured by light; difunctional methacrylates of C2-C30 monohydric or polyhydric alcohols that can be cured by light; and polyfunctional methacrylates of C3-C30 monohydric or polyhydric alcohols that can be cured by light. Component C is a photocrosslinking initiator.

5. The photocurable composition for encapsulation according to claim 4, characterized in that, The photocurable C1~C30 monohydric or polyhydric monofunctional methacrylate is any one or a combination of several of lauryl acrylate, ethoxyethyl acrylate, butyl acrylate, hydroxyethyl acrylate, isobornyl acrylate, tetrahydrofuran acrylate, methacrylate phosphate, and isobornyl methacrylate. The photocurable C2-C30 monohydric or polyhydric difunctional methacrylate is any one or a combination of several of the following: diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, propoxy neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, 20(ethoxy)bisphenol A diacrylate, and glycerol diacrylate. The photocurable C3-C30 monohydric or polyhydric alcohol polyfunctional methacrylate is any one or a combination of several of the following: trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane triol triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tripropylene acrylate, propoxylated pentaerythritol propylene acrylate, di(trimethylolpropane)tetraacrylate, triethylene glycol dimethacrylate, long-chain aliphatic hydrocarbon glycidyl ether acrylate, dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, phthalic acid diethanolate diacrylate, ethoxylated trimethylolpropane triol triacrylate, propoxylated trimethylolpropane triol triacrylate, propoxylated glycerol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, and ethoxylated neopentyl glycol methoxy monoacrylate. The photocrosslinking initiator is any one or a combination of several of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine ester.

6. A method for preparing the photocurable composition for encapsulation as described in claim 4, characterized in that, Includes the following steps: (1) Weigh each raw material according to the weight percentage of the photocurable composition for encapsulation, and set aside; (2) After mixing components A, B and C, the mixture is stirred under vacuum and filtered to obtain the photocurable composition for encapsulation.

7. The preparation method according to claim 6, characterized in that, The vacuum stirring temperature is 50℃ and the time is 80h.

8. An encapsulation film, characterized in that, The encapsulation film is formed by stacking inorganic and organic layers 1 to 5 times, with the outermost layer being inorganic. The organic layer is made of the photocurable composition for encapsulation as described in claim 4.

9. The encapsulation film according to claim 8, characterized in that, The inorganic layer material is selected from any one or a combination of several of silicon nitride, silicon oxynitride, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and zinc oxide, and has a thickness of 8~12μm.

10. A method for preparing an encapsulation film as described in claim 8, characterized in that, Includes the following steps: The inorganic layer is prepared by chemical vapor deposition, in which an inorganic layer material is coated onto the surface of the object to be encapsulated to form an inorganic layer. An organic layer is deposited on the inorganic layer by inkjet printing, and then cured by ultraviolet light to form an organic layer. This process is repeated, with the outermost layer being an inorganic layer, to obtain the encapsulation film.

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