Resin composition as well as preparation method and application thereof

Abstract

The invention provides a resin composition as well as a preparation method and application thereof, the resin composition comprises a first acrylate monomer and a second acrylate monomer, the first acrylate monomer contains a benzimidazole structure, the second acrylate monomer contains at least two C = C groups, the organic film formed by curing the resin composition has the properties of low curing shrinkage rate, strong adhesive force, high refractive index and the like.

Description

Technical Field

[0001] The invention relates to the field of organic electroluminescent devices, and in particular to a resin composition and a preparation method and application thereof. Background Art

[0002] Organic light-emitting diode (OLED) technology is widely used in advanced display devices and other fields due to its self-luminescence, wide viewing angle, full color and other characteristics. In order to prevent the internal devices of OLED from being corroded by oxygen and moisture in the air, which will cause the device life to decrease, it is usually necessary to encapsulate and protect it above the light-emitting layer. Inorganic materials such as silicon nitride and silicon oxynitride have good water and oxygen barrier effects and can be deposited on the light-emitting layer by vapor phase chemical deposition to form a protective layer. In order to further improve the toughness of the protective layer, a layer of resin is sprayed on the protective layer by inkjet printing, and then cured by ultraviolet (UV) irradiation to form an organic film.

[0003] Currently, polyacrylate compounds are mainly used as resin materials to form organic films. However, the organic films have problems such as large curing shrinkage, poor adhesion, and low refractive index. At the same time, the water and oxygen barrier properties of the organic films also need to be further improved.

[0004] Therefore, it is urgent to develop new resin materials so that the organic films they form have properties such as low curing shrinkage, strong adhesion, and high refractive index. Summary of the invention

[0005] The invention provides a resin composition and a preparation method and application thereof. The organic film formed by the resin composition after curing has a low curing shrinkage, high adhesion and high refractive index, thus overcoming the defects brought by the prior art.

[0006] One aspect of the present invention provides a resin composition, comprising a first acrylate monomer and a second acrylate monomer, wherein the first acrylate monomer contains a benzimidazole structure, and the second acrylate monomer contains at least two C=C groups.

[0007] According to one embodiment of the present invention, the structure of the first acrylate monomer is as shown in Formula 1:

[0008]

[0009] Wherein, R is selected from an alkyl group or an alkoxy group having 1 to 30 carbon atoms, and X is selected from an alkyl group or an alkoxy group having 1 to 30 carbon atoms, an alkyl group containing heteroatoms, an alkyl group containing aromatic rings, and an alkyl group containing aromatic heterocycles; and / or, the mass percentage of the first acrylate monomer in the resin composition is 20% to 70%.

[0010] According to one embodiment of the present invention, the first acrylate monomer includes one or more compounds having structures shown in Formula 2 to Formula 6:

[0011]

[0012] According to one embodiment of the present invention, the second acrylate monomer includes one or more of an acrylate monomer containing two C=C groups, an acrylate monomer containing three C=C groups, and an acrylate monomer containing more than three C=C groups; and / or the mass percentage of the second acrylate monomer in the resin composition is 20% to 70%.

[0013] According to one embodiment of the present invention, the structure of the acrylate monomer containing two C=C groups is shown in Formula 7:

[0014]

[0015] Wherein, Y1 and Y2 are independently selected from hydrogen atoms, alkyl groups having 1 to 30 carbon atoms, substituted alkyl groups, alkoxy groups, and substituted alkoxy groups, and Q is selected from alkyl groups having 1 to 30 carbon atoms, alkoxy groups, alkyl groups containing heteroatoms, alkyl groups containing aromatic rings, and alkyl groups containing aromatic heterocycles; and / or, the structure of the acrylate monomer containing three C=C groups is as shown in Formula 8:

[0016]

[0017] Among them, K1, K2, and K3 are independently selected from hydrogen atoms, alkyl groups with 1 to 30 carbon atoms, substituted alkyl groups, alkoxy groups, and substituted alkoxy groups; G1, G2, and G3 are independently selected from alkyl groups with 1 to 30 carbon atoms, alkoxy groups, alkyl groups containing heteroatoms, alkyl groups containing aromatic rings, and alkyl groups containing aromatic heterocycles; and / or, the acrylate monomer containing three or more C=C groups includes one or more acrylate monomers with 4 to 10 C=C groups.

[0018] According to one embodiment of the present invention, the resin composition further includes a photoinitiator and an auxiliary agent; and / or the resin composition satisfies: 2%≤(1-P1 / P2)*100%≤7%, wherein P1 is the density of the resin composition, and P2 is the density of a cured product formed by curing the resin composition.

[0019] According to one embodiment of the present invention, the photoinitiator includes one or more of alkyl phenones, acylphosphine oxides, benzophenones, heterothioxanthenes, and titanocenes; and / or, the mass percentage of the photoinitiator in the resin composition is 0.1% to 5%; and / or, the auxiliary agent includes one or more of a leveling agent, a defoamer, a coupling agent, a wetting and dispersing agent, an adhesion promoter, and a matting agent; and / or, the mass percentage of the auxiliary agent in the resin composition is 0.1% to 5%.

[0020] Another aspect of the present invention provides a method for preparing the above resin composition, comprising the following steps: mixing a first acrylate monomer, a second acrylate monomer, a photoinitiator, and an auxiliary agent to obtain the resin composition.

[0021] Another aspect of the present invention provides an organic film, comprising the above resin composition or a photocured product of the resin composition prepared according to the above method for preparing the resin composition.

[0022] According to one embodiment of the present invention, the refractive index of the organic film is 1.6 to 1.7; and / or the glass transition temperature of the organic film is 80°C to 100°C; and / or the strength of the organic film is 85MPa to 130MPa; and / or the modulus of the organic film is 1300MPa to 2000MPa; and / or the elongation at break of the organic film is 23% to 35%; and / or the water vapor permeability of the organic film is 2.5g / m 2 24h~4.0g / m 2 ·24h.

[0023] Another aspect of the present invention provides an organic electroluminescent device comprising the above organic film.

[0024] According to one embodiment of the present invention, the organic electroluminescent device further comprises a light-emitting layer and a protective layer, wherein the protective layer is located between the light-emitting layer and the organic film, and the protective layer comprises silicon nitride and / or silicon nitride oxide.

[0025] The implementation of the present invention has at least the following beneficial effects: the resin composition uses a first acrylate monomer containing a benzimidazole structure and a second acrylate monomer containing at least two C=C groups to form an organic film having a low curing shrinkage, high adhesion and high refractive index after curing. In addition, the organic film also has excellent mechanical properties, heat resistance and water and oxygen barrier properties. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] An embodiment of the present invention provides a resin composition, including a first acrylate monomer and a second acrylate monomer, wherein the first acrylate monomer contains a benzimidazole structure, and the second acrylate monomer contains at least two C=C groups.

[0028] According to the inventor's research, the benzimidazole structure in the first acrylate monomer can form a strong hydrogen bond interaction with silicon nitride or silicon oxynitride, thereby improving the adhesion of the organic film formed after the resin composition is cured, and the benzimidazole structure can form a strong intermolecular hydrogen bond with itself, thereby reducing the free volume of the resin composition after curing, so that the cured organic film has a lower curing shrinkage rate, and further improves the barrier ability of the organic film to water and oxygen. At the same time, the benzimidazole structure has a higher optical refractive index and can improve the refractive index of the organic film. The second acrylate monomer containing at least two C=C groups is beneficial to the curing of the resin composition, further improving the adhesion and refractive index of the organic film and reducing the curing shrinkage rate.

[0029] In some embodiments, the structure of the first acrylate monomer is as shown in Formula 1:

[0030]

[0031] Wherein, R is selected from alkyl and alkoxy groups having 1 to 30 carbon atoms (i.e., carbon chain length), and X is selected from alkyl and alkoxy groups having 1 to 30 carbon atoms, heteroatom-containing alkyl groups, aromatic ring-containing alkyl groups, and aromatic heterocyclic-containing alkyl groups.

[0032] In a specific implementation, R is selected from an alkyl group or an alkoxy group having 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 carbon atoms or any integer in the range of any two thereof, and X is selected from an alkyl group or an alkoxy group having 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 carbon atoms or any integer in the range of any two thereof, a heteroatom-containing alkyl group, an aromatic ring-containing alkyl group, and an aromatic heterocyclic ring-containing alkyl group.

[0033] In addition, the mass percentage of the first acrylate monomer in the resin composition is 20% to 70%, for example, 20%, 30%, 40%, 50%, 60%, 70% or a range composed of any two of them, which is beneficial to improving the adhesion, water and oxygen barrier capacity and refractive index of the organic film formed after the resin composition is cured, and reducing the curing shrinkage of the organic film.

[0034] In some embodiments, the first acrylate monomer includes one or more compounds having structures shown in Formula 2 to Formula 6:

[0035]

[0036] In some embodiments, the second acrylate monomer includes one or more of an acrylate monomer containing two C=C groups, an acrylate monomer containing three C=C groups, and an acrylate monomer containing more than three C=C groups.

[0037] In some embodiments, the mass percentage of the second acrylate monomer in the resin composition is 20% to 70%, for example, 20%, 30%, 40%, 50%, 60%, 70% or a range of any two thereof, which is beneficial to the curing of the resin composition, further improving the adhesion and refractive index of the organic film, and reducing the curing shrinkage.

[0038] In some embodiments, the structure of the acrylate monomer containing two C=C groups is shown in Formula 7:

[0039]

[0040] Wherein, Y1 and Y2 are independently selected from hydrogen atom, alkyl group with 1 to 30 carbon atoms, substituted alkyl group, alkoxy group, substituted alkoxy group, and Q is selected from alkyl group with 1 to 30 carbon atoms, alkoxy group, alkyl group containing heteroatoms, alkyl group containing aromatic rings, and alkyl group containing aromatic heterocycles.

[0041] Specifically, Y1 is selected from a hydrogen atom, an alkyl group having 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 carbon atoms or any integer in the range consisting of any two of them, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, Y2 is selected from a hydrogen atom, an alkyl group having 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 carbon atoms or any integer in the range consisting of any two of them, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and Q is selected from an alkyl group having 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 carbon atoms or any integer in the range consisting of any two of them, an alkoxy group, an alkyl group containing a heteroatom, an alkyl group containing an aromatic ring, and an alkyl group containing an aromatic heterocycle.

[0042] In specific implementation, the acrylate monomer containing two C=C groups (or bifunctional acrylate monomer) may include one or more of dipropylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, tetraethylene glycol diacrylate, dodecanediol dimethacrylate, tripropylene glycol diacrylate, and neopentyl glycol diacrylate.

[0043] In addition, the structure of the acrylate monomer containing three C=C groups is shown in Formula 8:

[0044]

[0045] Among them, K1, K2, and K3 are independently selected from hydrogen atoms, alkyl groups with 1 to 30 carbon atoms, substituted alkyl groups, alkoxy groups, and substituted alkoxy groups, and G1, G2, and G3 are independently selected from alkyl groups with 1 to 30 carbon atoms, alkoxy groups, alkyl groups containing heteroatoms, alkyl groups containing aromatic rings, and alkyl groups containing aromatic heterocycles.

[0046] Specifically, K1 is selected from a hydrogen atom, an alkyl group having a carbon number of 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 or any integer in the range of any two of them, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, K2 is selected from a hydrogen atom, an alkyl group having a carbon number of 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 or any integer in the range of any two of them, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, K3 is selected from a hydrogen atom, an alkyl group having a carbon number of 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 or any integer in the range of any two of them, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and G1 is selected from a , 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 or any integer in the range consisting of any two of them, alkyl, alkoxy, heteroatom-containing alkyl, aromatic ring-containing alkyl, aromatic heterocyclic ring-containing alkyl, G2 is selected from alkyl, alkoxy, heteroatom-containing alkyl, aromatic ring-containing alkyl, aromatic heterocyclic ring-containing alkyl having a carbon atom number of 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 or any integer in the range consisting of any two of them, G3 is selected from alkyl, alkoxy, heteroatom-containing alkyl, aromatic ring-containing alkyl, aromatic heterocyclic ring-containing alkyl having a carbon atom number of 1, 3, 5, 8, 10, 13, 15, 18, 20, 23, 25, 28, 30 or any integer in the range consisting of any two of them.

[0047] In specific implementation, the acrylate monomer containing three C=C groups (or trifunctional acrylate monomer) may include one or more of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, and melamine triacrylate.

[0048] In addition, the acrylate monomer containing three or more C=C groups includes one or more of acrylate monomers having 4 to 10 C=C groups, for example, one or more of acrylate monomers having 4, 5, 6, 7, 8, 9, and 10 C=C groups.

[0049] In specific implementation, the acrylate monomer containing three or more C=C groups (or multifunctional acrylate monomer) may include one or more of trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, alkoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and the like.

[0050] In some embodiments, the resin composition further includes a photoinitiator and an auxiliary agent, which is beneficial for the organic film formed after the resin composition is cured to maintain a high refractive index and high adhesion.

[0051] In some embodiments, the resin composition satisfies: 2%≤(1-P1 / P2)*100%≤7%, for example, 2%, 3%, 4%, 5%, 6%, 7% or a range consisting of any two of them, wherein P1 is the density of the resin composition, and P2 is the density of the cured product (i.e., the organic film) formed by curing the resin composition.

[0052] In some embodiments, the photoinitiator includes one or more of alkyl phenones, acylphosphine oxides, benzophenones, heterothioxanthones, and titanocenes.

[0053] Specifically, the alkyl phenones include one or more of the commercially available Omnirad 1173 (IGM, Japan) and Omnirad 184 (IGM, Japan), the acyl phosphorus oxides include one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate, the benzophenones include 4-phenylbenzophenone, the heterothioxanthones include one or more of Omnirad ITX (IGM, Japan) and Omnirad DETX (IGM, Japan); the titanocenes include the commercially available Omnirad 784 (IGM, Japan).

[0054] In addition, the mass percentage of the photoinitiator in the resin composition is 0.1% to 5%, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or any two thereof.

[0055] In some embodiments, the auxiliary agent includes one or more of a leveling agent, a defoaming agent, a coupling agent, a wetting and dispersing agent, an adhesion promoter, and a matting agent.

[0056] Specifically, the leveling agent includes one or more of the commercially available BYK-300 (Shin-Etsu, Japan), BYK-310 (BYK, Germany), BYK-307 (BYK, Germany), BYK-333 (BYK, Germany), and BYK-370 (BYK, Germany), and the defoaming agent includes one of the commercially available KS-66 (Shin-Etsu, Japan), KS-69 (Shin-Etsu, Japan), KS-108 (Shin-Etsu, Japan), BYK-070 (BYK, Germany), BYK-011 (BYK, Germany), BYK-012 (BYK, Germany), and BYK-057 (BYK, Germany). The coupling agent includes one or more of the commercially available KBM-403 (Shin-Etsu, Japan), KBM-503 (Shin-Etsu, Japan), and KBM-603 (Shin-Etsu, Japan). The wetting and dispersing agent includes one or more of the commercially available BYK-111 (BYK, Germany), BYK-142 (BYK, Germany), and BYK-145 (BYK, Germany). The adhesion promoter includes one or more of the commercially available BYK-4511 (BYK, Germany), BYK-4510 (BYK, Germany), BYK-4509 (BYK, Germany), and BYK-4512 (BYK, Germany). The matting agent includes ACEMATT One or more of HK125 (Evonik), ACEMATT HK400 (Evonik), ACEMATT HK440 (Evonik), ACEMATT OP278 (Evonik), ACEMATT HK450 (Evonik).

[0057] In addition, the mass percentage of the auxiliary agent in the resin composition is 0.1% to 5%, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or any two thereof.

[0058] An embodiment of the present invention further provides a method for preparing the above resin composition, comprising the following steps: mixing a first acrylate monomer, a second acrylate monomer, a photoinitiator, and an auxiliary agent to obtain a resin composition.

[0059] In a specific implementation, the first acrylate monomer, the second acrylate monomer, the photoinitiator and the auxiliary agent are added into a reaction kettle, stirred at room temperature (20°C-30°C) for 4h-6h, for example, 4h, 4.5h, 5h, 5.5h, 6h or a range consisting of any two thereof, and filtered to obtain a resin composition.

[0060] In the present invention, the preparation method of the above-mentioned resin composition does not affect the mass fractions of each component before and after preparation. For example, the ratio of the mass fraction of the first acrylate monomer to the total mass fraction of the first acrylate monomer, the second acrylate monomer, the photoinitiator, and the auxiliary agent is basically equal to the mass percentage of the first acrylate monomer in the resin composition.

[0061] An embodiment of the present invention further provides an organic film, comprising the above resin composition or a photocured product of the resin composition prepared by the above method for preparing the resin composition.

[0062] Specifically, the organic film is formed by curing the resin composition or a resin composition prepared according to the method for preparing the resin composition.

[0063] In a specific implementation, the resin composition is printed on the glass by inkjet printing to form a coating, and then ultraviolet light is cured to form an organic film.

[0064] In some embodiments, the refractive index of the organic film is 1.6 to 1.7, for example, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.7, or any range consisting of two thereof.

[0065] In addition, the glass transition temperature of the organic film is 80°C to 100°C, for example, 80°C, 81°C, 82°C, 85°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C or a range consisting of any two thereof.

[0066] In some embodiments, the strength of the organic film is 85 MPa to 130 MPa, for example, 85 MPa, 90 MPa, 95 MPa, 100 MPa, 105 MPa, 110 MPa, 115 MPa, 120 MPa, 125 MPa, 130 MPa or a range consisting of any two thereof.

[0067] Furthermore, the modulus of the organic film is 1300 MPa to 2000 MPa, for example, 1300 MPa, 1400 MPa, 1500 MPa, 1600 MPa, 1700 MPa, 1800 MPa, 1850 MPa, 1900 MPa, 1950 MPa, 2000 MPa, or a range consisting of any two thereof.

[0068] In some embodiments, the elongation at break of the organic film is 23% to 35%, for example, 23%, 25%, 28%, 30%, 33%, 35% or any two thereof.

[0069] In addition, the water vapor permeability of the organic film is 2.5g / m 2 24h~4.0g / m 2 24h, e.g. 2.5g / m 2 24h, 2.6g / m 2 24h, 2.7g / m 2 24h, 2.8g / m 2 24h, 2.9g / m 2 24h, 3.0g / m 2 24h, 3.1g / m 2 24h, 3.2g / m 2 24h, 3.3g / m 2 24h, 3.4g / m 2 24h, 3.5g / m 2 24h, 3.6g / m 2 24h, 3.7g / m 2 24h, 3.8g / m 2 24h, 3.9g / m 2 24h, 4.0g / m 2 ·24h or any combination of the two, which improves the water and oxygen barrier capacity of the organic film.

[0070] An embodiment of the present invention further provides an organic electroluminescent device, comprising the above-mentioned organic film.

[0071] In some embodiments, the organic electroluminescent device further includes a light-emitting layer and a protective layer. The protective layer is located between the light-emitting layer and the organic film to block corrosion from oxygen and moisture in the air, thereby extending the life of the organic electroluminescent device.

[0072] Generally, the protective layer includes inorganic materials, and the inorganic materials specifically include silicon nitride and / or silicon oxynitride, which are beneficial to inhibiting the erosion of oxygen and moisture in the air and prolonging the life of the organic electroluminescent device.

[0073] The present invention is further described below through specific embodiments.

[0074] Example 1

[0075] 40 parts by mass of the compound shown in Formula 2, 20 parts by mass of trimethylolpropane triacrylate, 20 parts by mass of ethoxylated bisphenol A diacrylate, 10 parts by mass of dipentaerythritol pentaacrylate, 5 parts by mass of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, and filtered to obtain a resin composition. The resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic film.

[0076] Example 2

[0077] 40 parts by mass of the compound shown in Formula 3, 20 parts by mass of trimethylolpropane triacrylate, 20 parts by mass of ethoxylated bisphenol A diacrylate, 10 parts by mass of dipentaerythritol pentaacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, filtered to obtain a resin composition, and the resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic film.

[0078] Example 3

[0079] 20 parts by mass of the compound shown in Formula 2, 30 parts by mass of trimethylolpropane triacrylate, 30 parts by mass of ethoxylated bisphenol A diacrylate, 10 parts by mass of dipentaerythritol pentaacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, and filtered to obtain a resin composition. The resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic sealing film.

[0080] Example 4

[0081] 50 parts by mass of the compound shown in Formula 2, 10 parts by mass of trimethylolpropane triacrylate, 20 parts by mass of ethoxylated bisphenol A diacrylate, 10 parts by mass of dipentaerythritol pentaacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, and filtered to obtain a resin composition. The resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic film.

[0082] Example 5

[0083] 30 parts by mass of the compound as shown in Formula 3, 10 parts by mass of pentaerythritol triacrylate, 50 parts by mass of dipentaerythritol pentaacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, and filtered to obtain a resin composition. The resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic film.

[0084] Example 6

[0085] 20 parts by mass of the compound represented by Formula 2, 20 parts by mass of the compound represented by Formula 3, 10 parts by mass of pentaerythritol triacrylate, 20 parts by mass of dipentaerythritol pentaacrylate, 20 parts by mass of pentaerythritol tetraacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, filtered to obtain a resin composition, and the resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic film.

[0086] Example 7

[0087] The difference from Example 1 is that the added amount of the compound shown in Formula 2 is 70 parts by mass, the added amount of trimethylolpropane triacrylate is 8 parts by mass, the added amount of ethoxylated bisphenol A diacrylate is 8 parts by mass, and the added amount of dipentaerythritol pentaacrylate is 4 parts by mass, and other conditions remain the same.

[0088] Example 8

[0089] The difference from Example 1 is that the added amount of the compound shown in Formula 2 is 80 parts by mass, the added amount of trimethylolpropane triacrylate is 4 parts by mass, the added amount of ethoxylated bisphenol A diacrylate is 4 parts by mass, and the added amount of dipentaerythritol pentaacrylate is 2 parts by mass, and other conditions remain the same.

[0090] Example 9

[0091] The difference from Example 1 is that the added amount of the compound shown in Formula 2 is 20 parts by mass, the added amount of trimethylolpropane triacrylate is 28 parts by mass, the added amount of ethoxylated bisphenol A diacrylate is 28 parts by mass, and the added amount of dipentaerythritol pentaacrylate is 14 parts by mass, and other conditions remain the same.

[0092] Example 10

[0093] The difference from Example 1 is that the added amount of the compound shown in Formula 2 is 10 parts by mass, the added amount of trimethylolpropane triacrylate is 32 parts by mass, the added amount of ethoxylated bisphenol A diacrylate is 32 parts by mass, and the added amount of dipentaerythritol pentaacrylate is 16 parts by mass, and other conditions remain the same.

[0094] Embodiment 11

[0095] The difference from Example 1 is that the compound shown in Formula 2 is changed to a compound shown in Formula 4, and other conditions remain the same.

[0096] Example 12

[0097] The difference from Example 1 is that the compound shown in Formula 2 is changed to a compound shown in Formula 5, and other conditions remain the same.

[0098] Embodiment 13

[0099] The difference from Example 1 is that the compound shown in Formula 2 is changed to a compound shown in Formula 6, and other conditions remain the same.

[0100] Comparative Example 1

[0101] 40 parts by mass of pentaerythritol triacrylate, 20 parts by mass of pentaerythritol pentaacrylate, 20 parts by mass of ethoxylated bisphenol A diacrylate, 10 parts by mass of trimethylolpropane triacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, and filtered to obtain a resin composition. The resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box at 1500 mj / cm 2 UV curing is carried out under conditions of to form an organic film.

[0102] Comparative Example 2

[0103] 20 parts by mass of pentaerythritol triacrylate, 30 parts by mass of pentaerythritol pentaacrylate, 40 parts by mass of ethoxylated bisphenol A diacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan) and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred at room temperature for 5 hours, and filtered to obtain a resin composition. The comparative resin composition was printed on ordinary glass to form a coating of 20 μm in thickness by inkjet printing, and further passed through a UV curing box at 1500 mJ / cm 2 UV curing is carried out under conditions of to form an organic film.

[0104] Comparative Example 3

[0105] 30 parts by mass of pentaerythritol triacrylate, 30 parts by mass of pentaerythritol pentaacrylate, 30 parts by mass of ethoxylated bisphenol A diacrylate, 5 parts by mass of TPO, 1 part by mass of BYK-307 (BYK, Germany), 2 parts by mass of KBM-403 (Shin-Etsu, Japan), and 2 parts by mass of BYK-4511 (BYK, Germany) were added into a reaction kettle, stirred for 5 hours at room temperature, and filtered to obtain a resin composition. The resin composition was printed on ordinary glass to form a 20 μm thick coating by inkjet printing, and further passed through a UV curing box to perform UV curing at 1500 mJ / cm2 to form an organic encapsulation layer.

[0106] Comparative Example 4

[0107] The difference from Example 1 is that the first acrylate monomer is not added, the added amount of trimethylolpropane triacrylate is 40 parts by mass, the added amount of ethoxylated bisphenol A diacrylate is 40 parts by mass, the added amount of dipentaerythritol pentaacrylate is 10 parts by mass, and other conditions remain the same.

[0108] The difference between Examples 2 to 13 and Example 1 is that the first acrylate monomer structural formula, the first acrylate mass fraction, the second acrylate type, and the second acrylate mass fraction are different, as shown in Table 1 for details.

[0109] The performance tests of the resin compositions and organic films in Examples 1 to 13 and Comparative Examples 1 to 4 were carried out respectively through the following processes. The results are shown in Table 2:

[0110] (1) Group conversion rate: The resin composition was tested by Fourier transform infrared spectroscopy at 1635 cm before and after curing. -1 The stretching vibration peak intensity of C=C at the position represents the group conversion rate, and the specific calculation method is shown in formula (a):

[0111]

[0112] C: group conversion rate;

[0113] V1: 1635cm before curing of resin composition -1 The corrected peak intensity of

[0114] V2: 1635cm after the resin composition is cured -1 The corrected peak intensity.

[0115] (2) Adhesion test: Use a grid cutter to cut the organic film in perpendicular directions until the glass substrate is exposed, and then use a soft brush to remove the surface cutting debris. Then adhere 3M's Scotch 610 tape to the grid pattern, press it with your fingers, and then peel the tape off the grid pattern. Observe the shedding of the organic film at the grid pattern to determine its adhesion level.

[0116] The judgment criteria are as follows: 5B-the cut edge is clear and smooth, and there is no shedding in the 100 grids; 4B-the shedding area within the 100 grids is ≤5%; 3B-the shedding area within the 100 grids is 5-15%; 2B-the shedding area within the 100 grids is 15-35%; 1B-the shedding area within the 100 grids is 35-65%; 0B-the shedding area within the 100 grids is greater than 65%.

[0117] (3) Refractive index test: The refractive index of the organic film is characterized by a HORIBA spectroscopic ellipsometer using a light source with a wavelength of 633 nm and recording the refractive index value.

[0118] (4) Water vapor transmission rate test: The water vapor transmission rate of the organic film with a thickness of 5 μm was tested by a water vapor transmission rate tester (Permatran-W3 / 33, Mocon Co., Ltd.) at 38.7° C. and 100% RH.

[0119] (5) Mechanical properties test: The tensile strength, elastic modulus and elongation at break of the organic encapsulation layer were tested by a DMA850 (TA Instrument) dynamic mechanical analyzer. The cured organic encapsulation layer was cut into rectangular strips with a length of 50 mm and a width of 5 mm, fixed on a tensile fixture, and stretched at a constant speed of 5 mm / min until the strip broke, and the tensile strength, elastic modulus and elongation at break values ​​were read.

[0120] (6) Heat resistance test: The glass transition temperature of the organic film was tested by a TA DMA850 (TA Instrument) dynamic mechanical analyzer. The cured organic film was cut into rectangular strips with a length of 50 mm and a width of 5 mm, fixed on a tensile fixture, and the glass transition temperature of the organic film was tested at a frequency of 1 Hz, an amplitude of 125%, and a heating rate of 10°C / min.

[0121] (7) Curing shrinkage test: The density of the resin composition before curing is measured by a pycnometer and recorded as P1. The density of the organic film after curing is measured by an analytical balance and recorded as P2. The curing shrinkage K is calculated by formula (b).

[0122]

[0123] Table 1

[0124]

[0125]

[0126] Table 2

[0127]

[0128] As can be seen from Table 2, relative to Comparative Examples 1 to 4, the resin compositions of Examples 1 to 13 include a first acrylate monomer containing a benzimidazole structure and a second acrylate monomer containing at least two C=C groups, which is beneficial to reducing the curing shrinkage of the organic film formed after curing, improving the adhesion and refractive index of the organic film, thereby improving its refractive index, and is beneficial to improving the mechanical properties, heat resistance and water and oxygen barrier capacity of the organic film.

[0129] Compared with Examples 8 and 10, Examples 1 to 7, 9, 11 to 13 control the mass percentage of the first acrylate monomer containing a benzimidazole structure to 20% to 70% of the resin composition. Specifically, Examples 1, 3, 4, 7, and 9 control the mass percentage of the first acrylate monomer containing a benzimidazole structure to 20% to 70% of the resin composition, thereby further reducing the curing shrinkage of the organic film formed after curing, improving the adhesion and refractive index of the organic film, and further improving its refractive index, mechanical properties, heat resistance, and water and oxygen barrier capabilities.

[0130] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A resin composition, characterized in that The invention comprises a first acrylate monomer and a second acrylate monomer, wherein the first acrylate monomer contains a benzimidazole structure, and the second acrylate monomer contains at least two C=C groups.

2. The resin composition according to claim 1, characterized in that The structure of the first acrylate monomer is shown in Formula 1: Wherein, R is selected from an alkyl group or an alkoxy group having 1 to 30 carbon atoms, and X is selected from an alkyl group or an alkoxy group having 1 to 30 carbon atoms, an alkyl group containing heteroatoms, an alkyl group containing aromatic rings, and an alkyl group containing aromatic heterocycles; And / or, the mass percentage of the first acrylate monomer in the resin composition is 20% to 70%.

3. The resin composition according to claim 2, characterized in that The first acrylate monomer includes one or more compounds having structures shown in Formula 2 to Formula 6:

4. The resin composition according to claim 1, characterized in that The second acrylate monomer includes one or more of an acrylate monomer containing two C=C groups, an acrylate monomer containing three C=C groups, and an acrylate monomer containing more than three C=C groups; And / or, the mass percentage of the second acrylate monomer in the resin composition is 20% to 70%.

5. The resin composition according to claim 4, characterized in that The structure of the acrylate monomer containing two C=C groups is shown in Formula 7: Wherein, Y1 and Y2 are independently selected from hydrogen atom, alkyl group with 1 to 30 carbon atoms, substituted alkyl group, alkoxy group, substituted alkoxy group, Q is selected from alkyl group with 1 to 30 carbon atoms, alkoxy group, alkyl group containing heteroatom, alkyl group containing aromatic ring, alkyl group containing heteroaromatic ring; And / or, the structure of the acrylate monomer containing three C=C groups is as shown in Formula 8: Wherein, K1, K2, and K3 are independently selected from hydrogen atoms, alkyl groups having 1 to 30 carbon atoms, substituted alkyl groups, alkoxy groups, and substituted alkoxy groups; G1, G2, and G3 are independently selected from alkyl groups having 1 to 30 carbon atoms, alkoxy groups, alkyl groups containing heteroatoms, alkyl groups containing aromatic rings, and alkyl groups containing aromatic heterocycles; And / or, the acrylate monomer containing three or more C=C groups includes one or more acrylate monomers having 4 to 10 C=C groups.

6. The resin composition according to claim 1, characterized in that The resin composition also includes a photoinitiator and an auxiliary agent; And / or, the resin composition satisfies: 2%≤(1-P1 / P2)*100%≤7%, wherein P1 is the density of the resin composition, and P2 is the density of a cured product formed by curing the resin composition.

7. The resin composition according to claim 6, characterized in that The photoinitiator includes one or more of alkyl phenones, acylphosphine oxides, benzophenones, thioxanthones, and titanocenes; And / or, the mass percentage of the photoinitiator in the resin composition is 0.1% to 5%; And / or, the auxiliary agent includes one or more of a leveling agent, a defoaming agent, a coupling agent, a wetting and dispersing agent, an adhesion promoter, and a matting agent; And / or, the mass percentage of the auxiliary agent in the resin composition is 0.1% to 5%.

8. A method for preparing the resin composition according to any one of claims 1 to 7, characterized in that: The following steps are involved: The first acrylate monomer, the second acrylate monomer, a photoinitiator and an auxiliary agent are mixed to obtain the resin composition.

9. An organic film, characterized in that: The invention relates to a photocured product of a resin composition comprising the resin composition according to any one of claims 1 to 7 or a resin composition prepared by the method for preparing the resin composition according to claim 8.

10. The organic film according to claim 9, characterized in that The refractive index of the organic film is 1.6 to 1.7; And / or, the glass transition temperature of the organic film is 80° C. to 100° C.; And / or, the strength of the organic film is 85MPa to 130MPa; And / or, the modulus of the organic film is 1300MPa to 2000MPa; And / or, the elongation at break of the organic film is 23% to 35%; And / or, the water vapor permeability of the organic film is 2.5 g / m 2 24h~4.0g / m 2 ·24h.

11. An organic electroluminescent device, characterized in that: Comprising the organic film according to claim 9 or 10.

12. The organic electroluminescent device according to claim 11, characterized in that: The organic electroluminescent device further comprises a light-emitting layer and a protective layer. The protective layer is located between the light-emitting layer and the organic film, and the protective layer comprises silicon nitride and / or silicon nitride oxide.

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