Acrylate containing calixarene structure, synthesis method thereof, low-dielectric thin film packaging ink prepared from acrylate, use method and application of low-dielectric thin film packaging ink

Abstract

The invention belongs to the technical field of thin film packaging materials, and particularly discloses acrylate containing a calixarene structure, a synthesis method of the acrylate, low-dielectric thin film packaging ink prepared from the acrylate, a use method of the low-dielectric thin film packaging ink and application of the low-dielectric thin film packaging ink. The thin film packaging ink comprises 10 to 30 parts of acrylate, 30 to 60 parts of a photocurable monomer, 10 to 30 parts of a bridge ring type photocurable monomer and 0.1 to 10 parts of a photoinitiator, wherein the acrylate adopts acrylate containing a calixarene structure; the photocurable monomer is a mixture of bifunctional acrylate and polyfunctional acrylate, and the mass ratio of the bifunctional acrylate to the polyfunctional acrylate is (1-2): (2-4). The film packaging ink has moderate viscosity and surface tension, and the formed organic barrier layer not only has high curing rate, high light transmittance, good heat resistance and low dielectric constant, but also has high Tg temperature, excellent flexibility and good adhesive force, is applied to electronic components, and can effectively block water and oxygen erosion and prolong the service life.

Description

Technical Field

[0001] The invention belongs to the technical field of thin film packaging materials, and in particular relates to an acrylate containing a calixarene structure, a synthesis method and a low-dielectric thin film packaging ink prepared therefrom, and a use method and application thereof. Background Art

[0002] Organic Light-Emitting Diodes (OLED) are light-emitting electronic devices with a sandwich structure. The advent and development of OLED display technology has prompted the rapid evolution of display panels towards lighter, thinner and more flexible trends, and has been widely used in recent years. However, during use, OLED devices are extremely susceptible to interference from water, oxygen and outgassing. Once in contact with water and oxygen, the luminous efficiency, working performance, stability and service life of the device will be sharply reduced, and may even cause the entire organic light-emitting diode device to fail. In view of this, a multi-layer thin film encapsulation process is usually used to encapsulate it, the purpose of which is to prevent the contact between organic molecular materials and air, thereby isolating it from external water and oxygen.

[0003] At present, the thin film encapsulation structure usually includes an inorganic barrier layer and an organic barrier layer constructed in sequence. The inorganic barrier layer is extremely dense and plays the core role of blocking water and oxygen. It is generally formed by plasma enhanced chemical vapor deposition (PECVD) with the help of inorganic materials. The organic barrier layer plays the role of toughening and buffering, and is mainly made of thin film organic compositions by inkjet printing. The materials selected for the thin film encapsulation structure will significantly affect the performance of OLED devices, which sets higher standards for the performance of thin film encapsulation materials. Among them, the dielectric constant of the organic barrier layer has also become one of the key factors. Once the dielectric constant of the material used is too high, it will cause the OLED device to form a larger signal-to-noise ratio and signal delay. Therefore, the development of thin film encapsulation materials with low dielectric constants has become an important node in flexible OLED encapsulation technology. In addition, for the film used to encapsulate organic light-emitting diodes, it is also necessary to have a high visible light transmittance to reduce the film's own absorption loss of the device's light emission; at the same time, when the film thickness is large, it is easy to crack after curing and the flexibility is poor, so better elongation at break and tensile strength are required, but existing thin film encapsulation materials are difficult to meet the above requirements at the same time.

[0004] In view of this, the present inventors provide an acrylate containing a calixarene structure, a synthesis method and a low dielectric thin film encapsulation ink prepared therefrom, a use method and an application thereof, so as to overcome the defects of the prior art. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide an acrylate containing a calixarene structure, a synthesis method and a low dielectric thin film encapsulation ink prepared therefrom, a method of using and an application thereof. By adopting the thin film encapsulation material (ink) prepared by the acrylate containing a calixarene structure provided by the present invention, not only the dielectric constant is reduced, but also high visible light transmittance, excellent elongation at break and tensile strength and excellent thermal stability can be simultaneously achieved.

[0006] The objective of the present invention is achieved through the following technical solutions:

[0007] In a first aspect, the present invention provides an acrylate containing a calixarene structure, wherein the general structural formula of the acrylate is shown in the following formula (1):

[0008]

[0009] Wherein, X is selected from H or tert-butyl, n is selected from 4, 5, 6 or 8; L is selected from H or the structure represented by the following formula (2):

[0010]

[0011] In formula (2), Y is selected from H, CH3, CH2CH3 or CF3; Z is selected from O, -ORO- or -NHRO-, and R in -ORO- or -NHRO- is selected from a C1 to C20 alkyl chain.

[0012] Furthermore, the acrylic acid ester includes any one of the structures shown in the following formulas (3) to (6):

[0013]

[0014]

[0015] In the second aspect, the present invention provides a method for synthesizing the above-mentioned acrylate containing a calixarene structure. The synthesis method first adds a calix[n]arene compound and a monomer containing an acrylate group into an organic solvent for dissolution; then reacts at a temperature of 50°C to 80°C for 24h to 48h to synthesize the target product.

[0016] Furthermore, the molar mass ratio of the calix[n]arene compound to the monomer containing an acrylate group is 1:0.2-0.8.

[0017] Furthermore, the calix[n]arene compound includes any one of calix[4]arene, calix[5]arene, calix[6]arene, calix[8]arene, p-tert-butylcalix[4]arene, p-tert-butylcalix[5]arene, p-tert-butylcalix[6]arene or p-tert-butylcalix[8]arene.

[0018] Further, the acrylate group-containing monomer includes any one of 3-bromo-1-propyl acrylate, 6-bromo-1-hexyl acrylate or acryloyl chloride;

[0019] The organic solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide or N,N-diethylformamide.

[0020] In a third aspect, the present invention provides a low dielectric thin film encapsulation ink, comprising the following raw materials, by weight: 10 to 30 parts of acrylate, 30 to 60 parts of photocurable monomer, 10 to 30 parts of bridged ring photocurable monomer and 0.1 to 10 parts of photoinitiator;

[0021] Wherein, the acrylate is the acrylate containing a calixarene structure described above or the acrylate containing a calixarene structure synthesized by the synthesis method described above. Such a configuration can make the thin film encapsulation ink achieve low dielectric while taking into account other properties such as high glass transition temperature and high transmittance.

[0022] Preferably, the film encapsulation ink comprises, by weight, 15 to 25 parts of acrylate, 40 to 50 parts of photocurable monomer, 15 to 25 parts of bridged ring photocurable monomer and 2 to 8 parts of photoinitiator.

[0023] Furthermore, the photocurable monomer is a silicon-containing or silicon-free long alkyl chain acrylate, containing 1 to 25 carbon atoms of a long alkyl chain acrylate, specifically a difunctional acrylate and a multifunctional acrylate, and the mass ratio of the difunctional acrylate to the multifunctional acrylate is (1-2): (2-4).

[0024] Among them, the bifunctional acrylate can be a silicon-containing or silicon-free bifunctional acrylate, and the bifunctional silicon-containing acrylate includes but is not limited to: 2-methyl-(diphenylsilylene) di-3,1-propylene glycol ester (CAS No.: 1581235-15-5); the bifunctional silicon-free acrylate includes but is not limited to: 2-methyl-2-acrylic acid-1,10-decanediol ester, di(methyl)acrylate dodecyl glycol ester, 1,4-butanediol dimethacrylate, 2-methyl-1,3-propylene glycol diacrylate, and ethylene glycol dimethacrylate.

[0025] The multifunctional group is a silicon-free acrylate, which includes but is not limited to any one of glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0026] Further, the bridged ring photocurable monomer includes but is not limited to bridged ring diacrylate monomers containing six to twenty-five carbon atoms, specifically: one or more of tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 6-bicyclo[2.2.1]heptyl methyl 2-methylprop-2-enoate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate 1-adamantyl (methyl)acrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxylated acrylate, dicyclopentenyl ethoxylated methacrylate, dicyclopentyl methacrylate and isobornyl acrylate.

[0027] It should be noted that the present invention improves the molecular rigidity by adding a bridge ring structure to the flexible cycloalkyl group. As a small molecule compound, the bridge ring type photocurable monomer has a relatively rigid bridge ring structure and two acrylate reaction sites, which can react with the acrylic acid group of the acrylate containing the calixarene structure during polymerization, promote the formation of a cross-linked network structure, increase the cross-linking density, and greatly improve the heat resistance.

[0028] Further, the photoinitiator includes one or more of TPO, TEPO, 1173, 184, 819, 4-methoxybenzaldehyde and 2,4-bis(trichloromethyl)-6-methyl-1,3,5-triazine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, hydroxybenzophenone, diphenylacetone, α-hydroxyalkylbenzophenone, α-aminoalkylbenzophenone, benzophenone, 2-methylbenzophenone, 2,4-dihydroxybenzophenone, thiopropoxythioxanthone, isopropylthioxanthone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, dibenzoylphenylphosphine oxide and benzoyldiphenylphosphine oxide.

[0029] According to actual measurements, the surface tension of the low dielectric thin film encapsulation ink provided by the present invention is 30 dyne / cm to 35 dyne / cm and the viscosity is 13 cps to 18 cps at a temperature of 25±5°C.

[0030] In a fourth aspect, the present invention provides a method for preparing a low dielectric thin film encapsulation ink, which is as follows: an acrylate containing a calixarene structure, a photocurable monomer, a bridge ring photocurable monomer and a photoinitiator are added into a container according to the above-mentioned mass ratio, and stirred for 30 minutes to 60 minutes in a light-proof condition, and allowed to stand for 40 minutes to 80 minutes.

[0031] In a fifth aspect, the present invention provides a method for using the above-mentioned low dielectric thin film encapsulation ink, comprising firstly attaching the low dielectric thin film encapsulation ink to the surface of the electronic device to be encapsulated by spin coating, scraping or inkjet printing; and then irradiating the low dielectric thin film encapsulation ink with ultraviolet light having a wavelength of 250nm to 400nm for 30s to 600s to solidify the ink to form an organic thin film with a thickness of 8μm to 15μm for protecting the electronic device;

[0032] The light transmittance of the organic thin film formed by curing reaches 95.5% to 99.7% at a wavelength of 400nm to 780nm, the dielectric constant is less than or equal to 2.55, and the dielectric loss is less than 0.05.

[0033] Furthermore, the power of the UV light is 10 mW / cm 2 ~500mW / cm 2 .

[0034] In a sixth aspect, the present invention also provides an application of the above-mentioned low dielectric thin film encapsulation ink, wherein the thin film encapsulation ink is used to prepare an organic barrier layer of electronic components, and the electronic components include organic light emitting diodes, photosensors, photovoltaic devices or integrated circuit boards.

[0035] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0036] 1. The film encapsulation ink provided by the present invention is mainly composed of a specific proportion of acrylate, a photocurable monomer, a bridge ring photocurable monomer and a photoinitiator. Among them, acrylate is synthesized by a calixarene compound, a monomer containing an acrylate group and an organic solvent, and calixarene is a calixarene oligomer composed of n phenol units, and its lower edge has four hydrophilic phenolic hydroxyl groups and a hydrophobic cavity, and the calixarene's own unique cavity structure and the introduction of large-volume alkanes can significantly increase the free volume of the molecule, and the calixarene structure is symmetrical, which reduces the molecular polarity. After the polar phenolic hydroxyl group fully reacts with the halogenated hydrocarbon containing acrylate, the molecular polarity of the phenolic hydroxyl group is further reduced, and the molecular polarity of the phenolic hydroxyl group is further reduced, thereby reducing the dielectric constant and dielectric loss of the acrylate containing the calixarene structure. Finally, the acrylate containing the calixarene structure and other monomers and initiators are compounded to obtain a low dielectric film encapsulation ink. After the ink is cured at 1MHz, the dielectric constant is 2.55 and the dielectric loss is 0.05. Compared with the prior art, the dielectric constant of the ink containing acrylate containing calixarene structure is reduced by 0.4 to 0.6. Therefore, the use of such thin film encapsulation ink can greatly improve the signal-to-noise ratio and signal delay of OLED devices.

[0037] 2. The thin film encapsulation ink provided by the present invention, the acrylate containing the cup aromatic structure and the photocurable monomer (silicon-containing or non-silicon-containing long alkyl chain acrylate) cooperate with each other to increase the free volume, while reducing the dielectric constant, ensuring the flexibility of the film, thereby optimizing the visible light transmittance of the cured film. In addition, this combination increases the overall carbon content, thereby increasing the glass transition temperature to 90°C to 150°C, enhancing the etching resistance, and effectively improving the adhesion of the substrate (reaching 2B to 3B). At the same time, the photocuring rate of the ink is above 95%, and it has a suitable viscosity (12cps to 18cps) and surface tension (30dyne / cm to 35dyne / cm). In other words, the thin film encapsulation ink provided by the present invention can take into account the above-mentioned multiple excellent properties at the same time.

[0038] 3. In the thin film encapsulation ink provided by the present invention, the acrylate containing a calixarene structure can cooperate with the bridge-ring photocurable monomer. Specifically, the bridge-ring photocurable monomer has a relatively rigid bridge-ring structure and two acrylic acid reaction sites, which can react with the acrylic acid group of the acrylate containing a calixarene structure during the polymerization process, promote the formation of a network structure, increase the cross-linking density, and thus improve the heat resistance. Cracking is prone to occur when the film thickness is large. To solve this problem, a method of increasing the flexibility of its main chain is adopted, and it is blended with the bridge-ring photocurable monomer at the same time. In this way, the cracking problem of the thick film is effectively solved, so that it has excellent flexibility (appropriate tensile strength and elongation at break) and good thermal stability. DETAILED DESCRIPTION

[0039] Here, exemplary embodiments will be described in detail. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Instead, they are only examples consistent with some aspects of the present invention as detailed in the appended claims.

[0040] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with embodiments.

[0041] Example 1 (This example uses an acrylate containing a calixarene structure of Formula 3)

[0042] The specific synthesis process of the acrylate containing a calixarene structure (Formula 3) in the embodiment of the present invention is as follows:

[0043] 24 g of sodium hydride (1 mol, 10 eq.) and 0.3 g of phenothiazine (1.5 mmol) were added to a 1000 ml three-necked flask equipped with a condenser, a magnet and a thermometer, and then 400 ml of dry N,N-dimethylformamide was poured in and stirred thoroughly to make it dispersed evenly. Then, 64.9 g of p-tert-butylcalix[4]arene (0.1 mol, 1 eq.) was added, stirred at 30°C for 1 hour, and then 141 g of 6-bromo-1-hexylacrylate (0.6 mol, 6 eq.) was added, heated to 50°C and reacted for 36 hours. After the reaction was completed, it was cooled to room temperature and filtered to obtain a filtrate. The obtained filtrate was evaporated by rotary evaporation to remove the solvent, and the obtained residue was dissolved in ethyl acetate and extracted with water. The organic layer was washed with saturated brine and dried by adding anhydrous magnesium sulfate. The organic layer was evaporated under reduced pressure on a rotary evaporator. The crude product was purified by a chromatographic column (n-hexane / ethyl acetate, 10:1) to finally obtain tert-butyl calix[4]arene tetrahexyl acrylate as shown in Formula 3 with a yield of 65%.

[0044] The results of NMR are 1 H NMR (400MHz, CDCl3, ppm) δ6.77(8H,ArH),6.40(4H,-CH=CH2),6.12(4H,-CH=CH2),5.81(4H,-CH=CH2),4.37(4H,ArCH2Ar),4.17(8H,–OCH2(CH2)4CH2O–),3.85( 8H,OCH2(CH2)4CH2O–),3.11(4H,ArCH2Ar),2.01(8H,–OCH2(CH2)4CH2O–),1.75 (8H,–OCH2(CH2)4CH2O–), 1.44(16H,–OCH2(CH2)4CH2O–), 1.08(36H,C(CH3)3). It is in good agreement with the theoretical value of 1:1, indicating that tert-butylcalix[4]arene tetrahexyl acrylate was successfully synthesized.

[0045] The low dielectric thin film encapsulation ink provided in this embodiment includes the following raw materials, by weight: 20 parts of acrylate containing a calixarene structure (Formula 3), 45 parts of a photocurable monomer, 10 parts of a bridged ring photocurable monomer, and 3 parts of a photoinitiator.

[0046] The photocurable monomer is a mixture of a bifunctional silicon-containing acrylate and a multifunctional silicon-free acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is 1: 2. Specifically, the bifunctional silicon-containing acrylate is 2-methyl-(diphenylsilylene)di-3,1-propylene glycol ester (CAS No.: 1581235-15-5), and the multifunctional silicon-free acrylate is trimethylolpropane tri(meth)acrylate.

[0047] The bridge ring photocurable monomer is tricyclo[5.2.1.02,6]dec-8-yl methacrylate.

[0048] The photoinitiator is 4,4'-dichlorobenzophenone.

[0049] According to the above ratio, acrylate containing calixarene structure, photocurable monomer, bridge ring photocurable monomer and photoinitiator are added into a stainless steel container, stirred for 30 minutes under light-proof conditions, and allowed to stand for 40 minutes to obtain a low dielectric thin film encapsulation ink; then, the obtained thin film encapsulation ink is applied to the surface of the substrate by inkjet printing, and the ink is sprayed with a wavelength of 250nm and a power of 10mW / cm 2 The film was cured by irradiation with UV light for 600 s to obtain a film with a thickness of 8 μm.

[0050] Example 2 (This example uses an acrylate containing a calixarene structure of Formula 4)

[0051] The specific synthesis process of the acrylate containing a calixarene structure (Formula 4) in the embodiment of the present invention is as follows:

[0052] 12 g of sodium hydride (0.5 mol, 5 eq.) and 0.3 g of phenothiazine (1.5 mmol) were added to a 1000 ml three-necked flask equipped with a condenser, a magnet and a thermometer, and then 400 ml of dry N,N-dimethylformamide was poured in and stirred thoroughly to make it dispersed evenly. Then, 64.9 g of p-tert-butylcalix[4]arene (0.1 mol, 1 eq.) was added and stirred at 30°C for 1 hour, followed by 71 g of 6-bromo-1-hexylacrylate (0.3 mol, 3 eq.), heated to 50°C and continued to react for 36 hours. After the reaction was completed, it was cooled to room temperature and filtered to obtain a filtrate. The obtained filtrate was evaporated by rotary evaporation to remove the solvent, and the obtained residue was dissolved in ethyl acetate and extracted with water. The organic layer was washed with saturated brine and dried by adding anhydrous magnesium sulfate. The organic layer was evaporated under reduced pressure on a rotary evaporator. The crude product was purified by a chromatographic column (n-hexane / ethyl acetate, 10:1) to finally obtain tert-butylcalix[4]arene dihexyl acrylate as shown in Formula 4 with a yield of 76%.

[0053] The low dielectric thin film encapsulation ink provided in this embodiment includes the following raw materials, by weight: 10 parts of acrylate containing a calixarene structure (Formula 3), 40 parts of a photocurable monomer, 15 parts of a bridged ring photocurable monomer, and 2 parts of a photoinitiator.

[0054] The photocurable monomer is a mixture of a bifunctional silicon-containing acrylate and a multifunctional silicon-free acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is 1: 1. Specifically, the bifunctional silicon-containing acrylate is 2-methyl-(diphenylsilylene)di-3,1-propylene glycol ester (CAS No.: 1581235-15-5), and the multifunctional silicon-free acrylate is pentaerythritol tri(meth)acrylate.

[0055] The bridge ring photocurable monomer is tricyclodecane dimethanol diacrylate.

[0056] The photoinitiator is a mixture of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide and hydroxybenzophenone, and the mass ratio of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide to hydroxybenzophenone is 1:1.

[0057] According to the above ratio, acrylate containing calixarene structure, photocurable monomer, bridge ring photocurable monomer and photoinitiator are added into a stainless steel container, stirred for 40 minutes under light-proof conditions, and allowed to stand for 50 minutes to obtain a low dielectric thin film encapsulation ink; then, the obtained thin film encapsulation ink is applied to the surface of the substrate by inkjet printing, and the ink is printed with a wavelength of 300nm and a power of 30mW / cm 2 The film was cured by irradiation with UV light for 550 s to obtain a film with a thickness of 10 μm.

[0058] Example 3 (This example uses acrylate containing a calixarene structure of Formula 5)

[0059] The specific synthesis process of the acrylate containing a calixarene structure (Formula 5) in the embodiment of the present invention is as follows:

[0060] 61 g of triethylamine (0.6 mol, 6 eq.) was added to a 1000 ml three-necked flask equipped with a condenser, a magnet, and a constant pressure bottom liquid funnel, and then 400 ml of dry dichloromethane was poured in, and the mixture was stirred thoroughly to disperse. Then 64.9 g of p-tert-butylcalix[4]arene (0.1 mol, 1 eq.) was added, and 54.3 g of acryloyl chloride (0.3 mol, 3 eq.) was added at 0°C, and then the mixture was returned to room temperature for reaction for 8 hours. After the reaction was completed, the reaction system was cooled to room temperature, and the filtrate was obtained by filtration. The obtained filtrate was evaporated by rotary evaporation to remove the solvent, and the obtained residue was dissolved in ethyl acetate and then extracted with water. The organic layer was washed with saturated brine, dried by adding anhydrous magnesium sulfate, and the organic layer was evaporated under reduced pressure by rotary evaporation. The obtained crude product was purified by column chromatography (n-hexane / ethyl acetate, 10:1), and finally 63 g of p-tert-butylcalix[4]arene tetraacrylate shown in formula 5 was obtained, with a yield of 73%.

[0061] The low dielectric thin film encapsulation ink provided in this embodiment includes the following raw materials, by weight: 20 parts of acrylate containing a calixarene structure (Formula 5), ​​30 parts of a photocurable monomer, 20 parts of a bridged ring photocurable monomer, and 5 parts of a photoinitiator.

[0062] The photocurable monomer is a mixture of a bifunctional non-silicone acrylate and a multifunctional non-silicone acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is 1:3. Specifically, the bifunctional non-silicone acrylate is 2-methyl-2-acrylic acid-1,10-decanediol; and the multifunctional non-silicone acrylate is glycerol tri(meth)acrylate.

[0063] The bridged ring photocurable monomer is selected from dicyclopentyl (meth)acrylate and 1-adamantyl (methyl) acrylate.

[0064] The photoinitiator is diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.

[0065] According to the above ratio, acrylate containing calixarene structure, photocurable monomer, bridge ring photocurable monomer and photoinitiator are added into a stainless steel container, stirred for 60 minutes under light-proof conditions, and allowed to stand for 80 minutes to obtain a low dielectric thin film encapsulation ink; then, the obtained thin film encapsulation ink is applied to the surface of the substrate by inkjet printing, and the ink is sprayed with a wavelength of 400nm and a power of 100mW / cm 2 The film was cured by irradiation with UV light for 60 s to obtain a film with a thickness of 12 μm.

[0066] Example 4 (This example uses acrylate containing a calixarene structure as Formula 6)

[0067] The specific synthesis process of the acrylate containing a calixarene structure (Formula 6) in the embodiment of the present invention is as follows:

[0068] 9.6 g of sodium hydride (0.4 mol, 4 eq.) and 0.1 g of phenothiazine (0.5 mmol) were added to a 1000 ml three-necked flask equipped with a condenser, a magnet and a thermometer, and then 400 ml of dry N,N-dimethylformamide was poured in and stirred thoroughly to make it dispersed evenly. Then, 63.7 g of calix[6]arene (0.1 mol, 1 eq.) was added thereto, stirred at 30°C for 1 hour, and then 57.9 g of 3-bromo-1-propyl acrylate (0.3 mol, 3 eq.) was added and heated to 50°C for 36 hours. After the reaction was completed, the reaction system was cooled to room temperature and the filtrate was obtained by filtering. The obtained filtrate was placed in a rotary evaporator for rotary evaporation to remove the solvent, and the obtained residue was dissolved in ethyl acetate and extracted with water. The organic layer was washed with saturated brine and dried by adding anhydrous magnesium sulfate. The organic layer was evaporated under reduced pressure using a rotary evaporator. The crude product was purified by a chromatographic column (n-hexane / ethyl acetate, 10:1) to finally obtain the calix[6]arene diacrylate shown in Formula 6 with a yield of 63%.

[0069] The low dielectric thin film encapsulation ink provided in this embodiment includes the following raw materials, by weight: 15 parts of acrylate containing a calixarene structure (Formula 6), 50 parts of a photocurable monomer, 25 parts of a bridged ring photocurable monomer, and 8 parts of a photoinitiator.

[0070] The photocurable monomer is a mixture of a bifunctional non-silicone acrylate and a multifunctional non-silicone acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is 1: 4. Specifically, the bifunctional non-silicone acrylate is dodecyl glycol di(meth)acrylate; and the multifunctional non-silicone acrylate is pentaerythritol tetra(meth)acrylate.

[0071] The bridge ring photocurable monomer is tricyclodecane dimethanol dimethacrylate.

[0072] The photoinitiator is benzophenone.

[0073] According to the above ratio, acrylate containing calixarene structure, photocurable monomer, bridge ring photocurable monomer and photoinitiator are added into a stainless steel container, stirred for 50 minutes under light-proof conditions, and allowed to stand for 60 minutes to obtain a low dielectric thin film encapsulation ink; then, the obtained thin film encapsulation ink is applied to the surface of the substrate by inkjet printing, and the ink is sprayed with a wavelength of 350nm and a power of 60mW / cm 2 The film was cured by irradiation with UV light for 500 s to obtain a film with a thickness of 15 μm.

[0074] Example 5 (This example uses acrylate containing a calixarene structure of Formula 3)

[0075] The acrylate containing a calixarene structure used in the present embodiment and embodiment 1 is of formula 3, and the difference between them is as follows:

[0076] The low dielectric thin film encapsulation ink provided in this embodiment includes the following raw materials, by weight: 30 parts of acrylate containing a calixarene structure (Formula 3), 60 parts of a photocurable monomer, 30 parts of a bridged ring photocurable monomer, and 5 parts of a photoinitiator.

[0077] The photocurable monomer is a mixture of a bifunctional silicon-containing acrylate and a multifunctional silicon-free acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is 2:3. Specifically, the bifunctional silicon-free acrylate is 1,4-butanediol dimethacrylate; and the multifunctional silicon-free acrylate is dipentaerythritol penta(meth)acrylate.

[0078] The bridge ring photocurable monomer is dicyclopentenyl ethoxylated acrylate.

[0079] The photoinitiator is 4,4'-bis(dimethylamino)benzophenone.

[0080] According to the above ratio, acrylate containing calixarene structure, photocurable monomer, bridge ring photocurable monomer and photoinitiator are added into a stainless steel container, stirred for 45 minutes under light-proof conditions, and allowed to stand for 55 minutes to obtain low dielectric thin film encapsulation ink; then, the obtained thin film encapsulation ink is applied to the surface of the substrate by inkjet printing, and the ink is sprayed with a wavelength of 300nm and a power of 500mW / cm 2 The film was cured by irradiation with UV light for 30 s to obtain a film with a thickness of 12 μm.

[0081] Example 6 (This example uses acrylate containing a calixarene structure of Formula 4)

[0082] The acrylate containing a calixarene structure used in the present embodiment and embodiment 2 is of formula 4, and the difference between them is as follows:

[0083] The low dielectric thin film encapsulation ink provided in this embodiment includes the following raw materials, by weight: 15 parts of acrylate containing a calixarene structure (Formula 4), 45 parts of a photocurable monomer, 30 parts of a bridged ring photocurable monomer, and 4 parts of a photoinitiator.

[0084] The photocurable monomer is a mixture of a bifunctional non-silicone acrylate and a multifunctional non-silicone acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is 1:4. Specifically, the bifunctional non-silicone acrylate is 2-methyl-1,3-propanediol diacrylate; and the multifunctional non-silicone acrylate is dipentaerythritol hexa(meth)acrylate.

[0085] The bridge ring photocurable monomer is isobornyl acrylate.

[0086] TPO was selected as the photoinitiator.

[0087] According to the above ratio, acrylate containing calixarene structure, photocurable monomer, bridge ring photocurable monomer and photoinitiator are added into a stainless steel container, stirred for 35 minutes under light-proof conditions, and allowed to stand for 45 minutes to obtain low dielectric thin film encapsulation ink; then, the obtained thin film encapsulation ink is applied to the surface of the substrate by inkjet printing, and the ink is printed with a wavelength of 400nm and a power of 60mW / cm 2 The film was cured by irradiation with UV light for 100 s to obtain a film with a thickness of 10 μm.

[0088] Comparative Example 1

[0089] The only difference between Comparative Example 1 and Example 1 is that, in the present comparative example, no acrylate containing a calixarene structure is added when preparing the thin film encapsulation ink.

[0090] Comparative Example 2

[0091] The only difference between Comparative Example 1 and Example 1 is that in the present comparative example, only 5 parts of acrylate containing a calixarene structure (Formula 3) are added when preparing the thin film encapsulation ink, that is, too little acrylate containing a calixarene structure is added.

[0092] Comparative Example 3

[0093] The only difference between Comparative Example 1 and Example 1 is that, in the present comparative example, 40 parts of acrylate containing a calixarene structure (Formula 3) are added when preparing the thin film encapsulation ink, that is, too much acrylate containing a calixarene structure is added.

[0094] Comparative Example 4

[0095] The only difference between Comparative Example 1 and Example 1 is that in the present comparative example, conventional acrylate containing aromatic hydrocarbons, such as m-phenoxybenzyl acrylate, is added when preparing the thin film encapsulation ink, that is, the added acrylate is not an acrylate containing a calixarene structure.

[0096] Comparative Example 5

[0097] The only difference between Comparative Example 1 and Example 2 is that, in the preparation of the thin film encapsulation ink in this comparative example, the photocurable monomers are a bifunctional silicon-containing acrylate and a multifunctional silicon-free acrylate, but the mass ratio of the two is 1:5.

[0098] In order to verify the efficacy of the present invention, the applicant conducted performance tests on the thin film encapsulation inks and the formed cured films prepared in Examples 1 to 6 and Comparative Examples 1 to 5, specifically including the following aspects:

[0099] (1) Surface tension: The surface tension was tested using a surface tension meter (QBZY-2 surface tension meter). The test was conducted at 25°C. Defoaming centrifugation was performed before the test. Each sample was tested 5 times and the final data was averaged.

[0100] (2) Viscosity: The viscosity of the high-refractive precursor solution was tested using a rotational rheometer (EVO type rotational viscometer). The test was performed at 25°C, using a 20 mm diameter conical rotor, and the shear rate was set to 0.01 s. -1 ~500s -1 , and select 10s -1 The viscosity of the samples under different shear rates was compared, and each sample was tested 5 times, and the final data was averaged.

[0101] (3) Refractive index: Pure organic inkjet printing with high refractive index ink was printed on a glass substrate and heated to 30 mW / cm in a nitrogen atmosphere. 2 The film was subjected to UV curing by UV irradiation under UV conditions to produce a cured film layer having a size of 5 mm×15 mm×0.1 mm (width×length×thickness), which was then tested using an Abbe refractometer.

[0102] (4) Light transmittance: Samples were prepared according to the method for forming a cured pattern except that no mask was used. The light transmittance of the cured film in the visible light range of 400 nm to 800 nm was measured using a UV-visible spectrophotometer (U-3900 Hitachi).

[0103] (5) Glass transition temperature (Tg): tested by differential scanning calorimetry (DSC), test conditions: test atmosphere N2 / O2; test temperature range: -180°C to 550°C; heating rate: 10°C / min.

[0104] (6) Photocuring rate: The encapsulation ink composition was inkjet printed on a glass substrate and subjected to a photocuring reaction at 30 mW / cm 2The sample was subjected to UV curing for 120 s by UV irradiation to produce a sample with a size of 3 cm × 7.5 cm × 18 μm (width × length × thickness), and then the encapsulant before curing and the film after curing were measured by FT-IR (Nicolet iS50, Thermo-Fisher) at 1635 cm -1 (C=C) and 1720cm -1 Absorption peak intensity near (C=O).

[0105] Photocuring rate (%) = |1-(F / S)| × 100;

[0106] Where F is the cured film at 1635cm -1 The absorption peak intensity near 1720cm -1 The ratio of the absorption peak intensities near 1635cm -1 The absorption peak intensity near 1720cm -1 The ratio of the absorption peak intensities near

[0107] (7) Dielectric constant: The dielectric constant of the TFE-INK composition was tested at 10 GHz using GB / T 1693-2007.

[0108] (8) Elongation at break: Based on GB / T 1040-92 "General test methods for mechanical properties of plastics (tensile)"; test conditions: tensile speed 1 mm / min, at least 5 specimens per group, and the average value of the test results. The sample size is a dumbbell-shaped specimen with a gauge length of 50 mm and a thickness of 10 μm.

[0109] (9) Tensile strength: Pure organic inkjet printing high refractive index ink was printed on a glass substrate and subjected to UV curing by UV irradiation at 30 mW / cm2 in a nitrogen atmosphere to prepare a cured film, which was measured in accordance with GB / T 1040-92 "General Test Method for Mechanical Properties of Plastics (Tensile)". Instrument: WDW-5A microcomputer-controlled electronic universal testing machine; Test conditions: tensile speed of 1 mm / min, at least 5 samples per group, and the test results were averaged.

[0110] After actual testing, the performance results of the thin film encapsulation ink and the formed cured film in each embodiment of the present invention and the comparative example are shown in Table 1 below:

[0111] Table 1

[0112]

[0113]

[0114] It can be known from the test results of Table 1 that the film encapsulation ink prepared by Examples 1 to 6 of the present invention with the help of a specific proportion of acrylate containing a calixarene structure, a photocurable monomer, a bridge-ring photocurable monomer and a photoinitiator has a viscosity and surface tension that is more suitable for inkjet printing. The curing rate and light transmittance of the prepared organic barrier layer photocurable adhesive are significantly improved, the dielectric constant is significantly reduced, and both can reach below 2.55, and the dielectric loss value is also reduced accordingly. At the same time, the acrylate containing a calixarene structure and the bridge-ring photocurable monomer cooperate with each other to increase the crosslinking density and thus improve the heat resistance, and also have a higher Tg temperature (90°C to 150°C) and excellent flexibility (appropriate tensile strength and elongation at break). In addition, the adhesion test was carried out by the hundred-grid slicing method, and the adhesion of Examples (2B to 3B) was enhanced compared to that of Comparative Example (1B).

[0115] However, the test results of Comparative Examples 1 to 3 show that if the acrylate containing a calixarene structure is not added to the formula, or the amount of the acrylate containing a calixarene structure added is too much or too little, the dielectric constant cannot be effectively reduced, and the transmittance, surface tension and viscosity do not meet the printing requirements, and the glass transition temperature, elongation at break and tensile strength also decrease. The test results of Comparative Example 4 show that when conventional acrylate containing aromatics, such as m-phenoxybenzyl acrylate, is used to replace the acrylate containing a calixarene structure, the curing rate of the obtained organic barrier layer photocurable adhesive is reduced, and the surface tension and viscosity are not within the appropriate range, which is not suitable for inkjet printing. In Comparative Example 5, the mass ratio of the bifunctional silicon-containing acrylate to the multifunctional non-silicon-containing acrylate is 1:5, which is not within the ratio given in the present invention (the mass ratio of the bifunctional acrylate to the multifunctional acrylate is (1-2): (2-4)), and a printing ink with low dielectric properties cannot be obtained.

[0116] The above description is only a specific embodiment of the present invention, so that those skilled in the art can understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention.

[0117] It should be understood that the present invention is not limited to what has been described above and that various modifications and changes may be made without departing from its scope. The scope of the present invention is limited only by the appended claims.

Claims

1. An acrylate containing a calixarene structure, characterized in that: The general structural formula of the acrylic acid ester is shown in the following formula (1): Wherein, X is selected from H or tert-butyl, n is selected from 4, 5, 6 or 8; L is selected from H or the structure represented by the following formula (2): In formula (2), Y is selected from H, CH3, CH2CH3 or CF3; Z is selected from O, -ORO- or -NHRO-, and R in -ORO- or -NHRO- is selected from a C1 to C20 alkyl chain.

2. The acrylate containing a calixarene structure according to claim 1, characterized in that: The acrylate includes any one of the structures shown in the following formulas (3) to (6):

3. The method for synthesizing an acrylic ester containing a calixarene structure according to claim 1 or 2, characterized in that: The synthesis method first adds a calix[n]arene compound and a monomer containing an acrylate group into an organic solvent to dissolve; then reacts at a temperature of 50° C. to 80° C. for 24 h to 48 h to synthesize the target product.

4. The synthesis method according to claim 3, characterized in that The molar mass ratio of the calix[n]arene compound to the monomer containing an acrylate group is 1:0.2-0.

8.

5. The synthesis method according to claim 3, characterized in that The calix[n]arene compound includes any one of calix[4]arene, calix[5]arene, calix[6]arene, calix[8]arene, p-tert-butylcalix[4]arene, p-tert-butylcalix[5]arene, p-tert-butylcalix[6]arene or p-tert-butylcalix[8]arene.

6. The synthesis method according to claim 3, characterized in that The acrylate-containing monomer includes any one of 3-bromo-1-propyl acrylate, 6-bromo-1-hexyl acrylate or acryloyl chloride; The organic solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide or N,N-diethylformamide.

7. A low dielectric thin film encapsulation ink, characterized in that: The raw materials include, by weight: 10 to 30 parts of acrylate, 30 to 60 parts of photocurable monomer, 10 to 30 parts of bridge ring photocurable monomer and 0.1 to 10 parts of photoinitiator; Wherein, the acrylate is the acrylate containing a calixarene structure as claimed in claim 1 or 2, or the acrylate containing a calixarene structure synthesized by the synthesis method as claimed in any one of claims 3 to 6.

8. The low dielectric thin film encapsulation ink according to claim 7, characterized in that: The photocurable monomer is a mixture of bifunctional acrylate and multifunctional acrylate, and the mass ratio of the bifunctional acrylate to the multifunctional acrylate is (1-2):(2-4).

9. The method for using the low dielectric thin film encapsulation ink according to claim 7 or 8, characterized in that: The method comprises firstly attaching the low dielectric thin film encapsulation ink to the surface of the electronic device to be encapsulated by spin coating, scraping or inkjet printing; and then irradiating the ink with ultraviolet light having a wavelength of 250nm to 400nm for 30s to 600s to solidify the ink to form an organic thin film with a thickness of 8μm to 15μm for protecting the electronic device; The light transmittance of the organic thin film formed by curing reaches 95.5% to 99.7% at a wavelength of 400nm to 780nm, the dielectric constant is less than or equal to 2.55, and the dielectric loss is less than 0.

05.

10. The use of the low dielectric thin film encapsulation ink according to claim 7 or 8, characterized in that: The thin film encapsulation ink is used to prepare an organic barrier layer of electronic components, and the electronic components include organic light emitting diodes, photosensitive sensors, photovoltaic devices or integrated circuit boards.

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