Fluoroaryl compound, preparation method, packaging ink composition containing fluoroaryl compound, use method and application

Abstract

The invention belongs to the technical field of organic thin films, and particularly discloses a fluoro-aryl compound, a preparation method, a packaging ink composition containing the fluoro-aryl compound, a use method and application, and the ink composition comprises the following components in parts by mass: 10-70 parts of an ultraviolet curable monomer, 1-10 parts of a photo-crosslinking initiator and 5-50 parts of the fluoro-aryl compound; wherein the ultraviolet curable monomer is a mixture of (methyl) acrylate containing a long carbon chain and a bridged ring photocurable monomer, and the mass ratio of the (methyl) acrylate to the bridged ring photocurable monomer is (20-45): (10-30). The ink composition containing the fluoroaryl compound provided by the invention not only can greatly reduce the dielectric constant, but also has the advantages of high curing rate, high light transmittance, high refractive index, high heat resistance, good bending performance after curing, capability of effectively blocking water and oxygen and the like, and provides material support for reliable packaging of electronic devices.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic thin films, and in particular relates to a fluorinated aromatic compound, a preparation method, a packaging ink composition containing the fluorinated aromatic compound, a use method and an application thereof. Background Art

[0002] Organic Light-Emitting Diode (OLED) is a device that uses a multi-layer organic thin film structure to generate electroluminescence. It has outstanding advantages such as easy production, low driving voltage, light weight, high brightness, low power consumption, fast response, high clarity, good flexibility, and high luminous efficiency. It can well meet consumers' new demands for display technology.

[0003] However, the performance and life of OLEDs are easily affected by external moisture and oxygen. When water vapor and oxygen enter the organic light-emitting material layer, they easily react chemically with the small molecules therein, causing the entire OLED device to fail. Therefore, how to better ensure the stability of OLEDs has become an important issue in the current preparation of OLED devices, and thin-film encapsulation technology is one of the better means to solve this problem. When using thin-film encapsulation of OLED devices, the device places more stringent requirements on the dielectric constant of the encapsulation medium material. This is because reducing the dielectric properties of the thin-film encapsulation material can effectively improve the touch performance of the device during use, and encapsulation materials with low dielectric constants can effectively reduce the delay effect of touch.

[0004] At present, there have been some reports on relevant low-dielectric-constant photocurable encapsulation compositions, such as an ink composition disclosed in China Publication No. CN115109464B, which includes a photocurable silicon-containing monomer, a reactive diluent and a photoinitiator. The fluorine-substituted silicon-containing monomer is used in combination with the reactive diluent to effectively reduce the dielectric constant, but it can only be reduced to 2.7, and the photocuring rate and transmittance cannot reach the optimal value. In other words, the technical problems existing in existing encapsulation materials are mainly: the dielectric constant is not low enough. Although existing technologies have tried to reduce the dielectric constant of encapsulation inks, they still cannot meet higher requirements; the photocuring rate and transmittance are not optimal, which affects the performance of the encapsulation material; it is difficult to achieve a good balance between the various properties of the encapsulation material, for example, the coordination between the properties such as flexibility, tensile strength, and viscosity still needs to be improved.

[0005] In view of this, this invention is proposed. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a fluorinated aromatic compound, a preparation method, a packaging ink composition comprising the same, a use method and an application, which are mainly used to solve the problems that the dielectric constant of existing packaging materials is not low enough, the photocuring rate and light transmittance are not optimal, and it is difficult to achieve a good balance between various properties.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a fluorinated aryl compound, the structure of which is shown in the following general formula (1):

[0009]

[0010] Wherein, PAHs in the general formula (1) represents polycyclic aromatic hydrocarbons, which refers to substituted or unsubstituted aromatic hydrocarbons containing two or more benzene rings, and at least one group on each aromatic hydrocarbon is substituted by L or Z; the L and Z are each independently selected from any one of H, F, CFH2, CF2H, CF3, C1-C12 fatty chain alkyl, C1-C12 fluoroalkyl and the groups shown in the following general formula (2), and at least one group among L and Z is a fluorine-containing group, and the fluorine-containing group is any one of F, CFH2, CF2H, CF3, C1-C12 fluoroalkyl and the groups shown in the following general formula (2);

[0011]

[0012] In the general formula (1) and the general formula (2), X is independently selected from one of F and CF3, Y is selected from one of -ORO- and -NHRO-, and R in the -ORO- or -NHRO- is selected from one of C0-C12 substituted or unsubstituted aliphatic chain alkyl, C3-C6 substituted or unsubstituted aliphatic cycloalkyl, and C6-C30 substituted or unsubstituted aryl.

[0013] The polycyclic aromatic hydrocarbons used in the present invention mainly have two combinations, one is a non-condensed ring type, including any one of biphenyl, biphenyl and polyphenylated aliphatic hydrocarbons; the other is a condensed ring type, that is, two carbon atoms are shared by two benzene rings, including but not limited to one of benzene, naphthalene, phenanthrene, anthracene, and pyrene.

[0014] Furthermore, the structure of the fluorinated aromatic compound includes at least one of the following formulas (1) to (10):

[0015]

[0016] In a second aspect, the present invention provides a method for preparing the above-mentioned fluorinated aromatic compound, which is carried out in two steps under the protection of an inert gas. First, a fluoroacrylic acid raw material, an acyl chloride raw material, a solvent and a catalyst are uniformly mixed according to a set ratio to obtain a fluoroacryloyl chloride product after reaction; then, the fluoroacryloyl chloride product obtained above is added dropwise to a solution formed by an alcohol or phenol raw material containing fluorine atoms and an organic base, and after reaction and subsequent treatment, the target product is obtained.

[0017] Furthermore, the molar ratio of the fluoroacrylic acid raw material to the acyl chloride raw material is 1:(2-4);

[0018] The molar ratio of the alcohol or phenol raw material containing fluorine atoms to the fluoroacryloyl chloride product is 1:(2-4).

[0019] The fluoroacrylic acid raw material includes trifluoromethylacrylic acid or 2-fluoroacrylic acid;

[0020] The acyl chloride raw material includes oxalyl chloride;

[0021] The alcohol or phenol raw material containing fluorine atoms includes (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethanol, 5-fluoronaphthalene-1-ol or perfluorobenzene-1-ol;

[0022] The solvent includes anhydrous dichloromethane or anhydrous ethyl acetate;

[0023] The catalyst includes N,N-dimethylformamide.

[0024] Furthermore, in the first step of preparing fluoroacryloyl chloride products, the reaction time at room temperature is 3h to 8h; in the second step, when the fluoroaryl compound is added dropwise to the solution, it should be carried out under low temperature (about 0°C), and after the reaction, the solution is neutralized with dilute hydrochloric acid; then, the neutralized solution is washed with a saturated sodium bicarbonate solution of the aqueous phase; then, the organic phase is removed, and the aqueous phase is extracted with ethyl acetate; thereafter, the organic solutions are combined and distilled for the first time to reduce the volume; finally, the remaining substance is purified by silica gel column chromatography, and finally the purified product is distilled again to obtain the target product.

[0025] It should be noted that the fluorinated aromatic compounds prepared by the present invention have unique structural characteristics, such as the presence of more fluorinated groups and specific phenyl structures. The introduction of fluorinated groups can effectively reduce the polarizability of molecules. Under the action of the electric field, the degree of molecular polarization is closely related to the induced dipole moment generated. When the degree of molecular polarization is lower, the induced dipole moment generated is smaller, thereby significantly reducing the dielectric properties of the material. In addition, the special chemical structure of the fluorinated aromatic compound has a unique influence in the encapsulation ink system. In general organic materials, strong intermolecular interactions will lead to a closer arrangement of molecules, thereby increasing dielectric properties; however, the presence of this new compound will interfere with the close arrangement of other molecules in the ink, increase the gaps between molecules, reduce intermolecular interactions, and thus reduce the dielectric constant of the material.

[0026] In addition, the fluoroaryl compound in the present invention contains an acrylate structure, and this special structure gives it certain non-polar characteristics. When a substance containing the compound is added to a packaging ink, the polarity of the ink as a whole can be changed. According to relevant principles, the dielectric constant of non-polar materials is usually low. Therefore, by adjusting the polarity of the ink to make it closer to a non-polar state, the dielectric properties of the packaging ink can be effectively reduced. This characteristic makes the fluoroaryl compound have important application value in the field of packaging inks, and provides an effective solution for achieving packaging inks with low dielectric properties.

[0027] In a third aspect, the present invention provides an encapsulation ink composition comprising the above-mentioned fluorinated aromatic compound, comprising the following raw materials in parts by mass: 10 to 70 parts of an ultraviolet light-curable monomer, 1 to 10 parts of a photocrosslinking initiator and 5 to 50 parts of a fluorinated aromatic compound.

[0028] Preferably, the ink composition has a formula of: 20 to 35 parts of an ultraviolet light curable monomer, 2 to 5 parts of a photocrosslinking initiator, and 30 to 65 parts of a fluorinated aromatic compound.

[0029] Furthermore, the UV-curable monomer is a mixture of a (meth)acrylate containing a long carbon chain and a bridge-ring photocurable monomer, and the mass ratio of the (meth)acrylate containing a long carbon chain to the bridge-ring photocurable monomer is (20-45): (10-30).

[0030] Specifically, the (meth)acrylate containing a long carbon chain includes one or more of 1,6-hexanediol diacrylate, 2-methyl-2-acrylate-1,10-decanediol, 2-methyl-2-acrylate-1,9-nonanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,11-undecanediol dimethacrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol dimethacrylate, 1,14-tetradecanediol di(meth)acrylate, and 1,18-octadecanediol dimethacrylate.

[0031] The bridged ring photocurable monomers include but are not limited to bridged ring diacrylate monomers containing six to twenty-five carbon atoms, specifically one or more of dicyclopentenyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, dicyclopentenyl ethoxylated acrylate, dicyclopentenyl ethoxylated methacrylate, isobornyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0032] The glass transition temperature (Tg) of the bridged ring photocurable monomer is generally 70°C to 180°C, but in the present invention, it is preferably greater than 90°C to increase the overall Tg of the system.

[0033] It should be noted that the present invention uses (meth) acrylates containing long carbon chains, which has the advantage of ensuring the flexibility of the encapsulation ink composition (ink) molecule. On this basis, the addition of bridge ring photocurable monomers greatly improves the molecular rigidity. The bridge ring photocurable monomers have a relatively rigid bridge ring structure and two acrylate reaction sites, which can react with the acrylic acid group of the fluorinated aryl compound during polymerization, thereby promoting the formation of a cross-linked network structure. The formation of this cross-linked network structure significantly increases the cross-linking density, which greatly improves the heat resistance. At the same time, the selection of high Tg (greater than 90°C) bridge ring photocurable monomers effectively avoids the phenomenon that the ink is too soft and cannot be used normally due to the addition of too much (meth) acrylate containing long carbon chains. The addition of bridge ring photocurable monomers can increase the Tg of the system, so that the thermal stability of the cured ink is improved. In addition, the fluorinated aryl compound cooperates with the bridge ring photocurable monomer to effectively reduce the dielectric constant and dielectric loss, and improve the light transmittance of the cured film.

[0034] Among them, (meth)acrylates containing long carbon chains have relatively strong intermolecular entanglement and interaction due to their long carbon chain structure, which will increase the viscosity of the ink. The structural complexity of bridge-type photocurable monomers will also have a certain impact on the viscosity. The presence of fluorinated aromatic compounds reduces the interaction between molecules, and to a certain extent can reduce the high viscosity effect brought by (meth)acrylates containing long carbon chains and bridge-type photocurable monomers. The present invention can obtain a suitable viscosity range by adjusting the ratio of the three, which can not only ensure the fluidity of the ink during the printing process, but also prevent the occurrence of sagging. In addition, (meth)acrylates containing long carbon chains usually have good flexibility and can improve the elongation at break of the ink. The structural rigidity of bridge-type photocurable monomers may increase the tensile strength. The presence of fluorinated aromatic compounds will increase the interaction between molecules. Under the joint action of the three, the elongation at break and the tensile strength of the encapsulated ink are balanced by adjusting the ratio. A higher elongation at break can make the ink have better toughness and not easy to break when subjected to external forces; a higher tensile strength can ensure the strength and stability of the ink during use.

[0035] Further, the photocrosslinking initiator includes one or more of TPO, TEPO, 1173, 184, 819, 4-methoxybenzaldehyde, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, hydroxybenzophenone, dibenzoylphenylphosphine oxide and benzoyldiphenylphosphine oxide.

[0036] After actual testing, the ink composition formed by the present invention has a surface tension of 29 dyne / cm to 33 dyne / cm at a temperature of 25±5°C, a viscosity of 18 cps to 25 cps, is suitable for inkjet printing, and has a dielectric constant of only 2.4 to 2.6.

[0037] In a fourth aspect, the present invention provides a method for using the above-mentioned encapsulation ink composition, and the specific steps are as follows:

[0038] Step 1) firstly attaching the ink composition to the surface of the electronic device to be packaged by spin coating, doctor blade coating, screen printing or inkjet printing;

[0039] Step 2) irradiating the ink composition with ultraviolet light having a wavelength of 250 nm to 400 nm for 30 s to 600 s, and finally curing the ink composition to form an organic film of 5 μm to 55 μm.

[0040] In a fifth aspect, the present invention also provides an application of the above-mentioned encapsulation ink composition in the preparation of an organic barrier film for waterproofing and oxygen-blocking electronic components, wherein the electronic components include other electronic devices such as organic light-emitting diodes, photosensors, or photovoltaic devices.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] 1. The fluorinated aromatic compound provided by the present invention can reduce the molecular polarizability. Therefore, after the substance is added to the encapsulated ink system, the polarizability of the molecule can be reduced, the response to the electric field can be reduced, and thus the dielectric properties of the composition can be reduced. At the same time, the substance can also interfere with the close arrangement of other molecules in the ink, increase the intermolecular gap, reduce the interaction, and reduce the dielectric constant. In addition, it can change the overall polarity of the ink, making it close to non-polar, and effectively reduce the dielectric properties of the encapsulated ink. The dielectric constant is as low as 2.41 after actual testing. The low dielectric constant can reduce signal transmission delay and loss and improve the performance of electronic equipment.

[0043] 2. In the ink composition formed by the fluorinated aromatic compound of the present invention, the fluorinated aromatic compound increases the intermolecular interaction force, and the high Tg (greater than 90°C) bridge-type photocurable monomer improves the thermal stability of the encapsulated ink. At the same time, the higher glass transition temperature also improves the heat resistance and dimensional stability of the ink. According to actual tests, the photocuring rate of the ink composition is above 98%, and it has a suitable viscosity (18cps~25cps) and surface tension (29dyne / cm~33dyne / cm), taking into account excellent printing performance.

[0044] 3. The UV-curable monomer of the present invention is a mixture of a (meth)acrylate containing a long carbon chain and a bridged ring photocurable monomer, and has specific requirements for the ratio of the two to be added, so as to exert the synergistic effect of the two. Finally, by adjusting the ratio of the three, the photocrosslinking initiator and the fluorinated aromatic compound, a suitable viscosity range can be obtained, which not only ensures the fluidity of the ink during the printing process, but also prevents the occurrence of sagging, effectively solves the problem of thick film cracking, and enables the composition to have excellent flexibility (appropriate tensile strength and elongation at break) and good thermal stability.

[0045] 4. The ink composition provided by the present invention has a maximum refractive index of only 1.56 through actual testing, that is, by adjusting the refractive index to reduce interface reflection, the transmittance is further improved (higher than 98%). In addition, the difficulty and risk of the inkjet printing process are reduced, the optical effect is more excellent, the curing rate is fast, and the film layer formed after curing has high transmittance and high bending resistance, which is suitable for application scenarios that require bending and folding. DETAILED DESCRIPTION

[0046] Here, exemplary embodiments will be described in detail, and 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 described in detail in the appended claims.

[0047] 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 relevant experiments.

[0048] Preparation Example 1 (Synthesis of (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethyl-2-(trifluoromethyl)acrylate represented by the following formula (1))

[0049]

[0050] The specific synthesis process is as follows:

[0051] 1) At 25 degrees Celsius and in a nitrogen atmosphere, 68.0 grams of oxalyl chloride were added dropwise to a solution containing 50.0 grams (386 millimoles) of trifluoromethylacrylic acid and 90 milliliters of dichloromethane, and finally a catalytic amount of N,N-dimethylformamide was added. The reaction mixture was heated to reflux at 50 degrees Celsius for 5 hours, and then the solvent and excess reagents were removed and concentrated using a rotary evaporator to obtain 2-trifluoromethylacryloyl chloride as a yellow liquid, which was directly used for the next step without purification.

[0052] 2) Add 122.0 g of (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethanol (CAS: 127852-28-2) to a 1000 ml three-necked round-bottom flask equipped with a magnetic stirrer and a constant pressure dropping funnel, and use a double-row tube to perform vacuum and nitrogen filling operations three times. Under a nitrogen atmosphere, add 500 ml of anhydrous dichloromethane and 40.0 g, 38 ml of pyridine, and then cool the reaction system to 0°C. Take the 2-trifluoromethylacryloyl chloride obtained in the previous step and add it to the constant pressure dropping funnel. Slowly add the mixed solution to the 0°C reaction system at a rate of 1 drop / second, and stir vigorously to ensure that the acid chloride is dispersed in time and fully. After the dropwise addition is completed, the mixture is stirred at room temperature overnight to react. After the reaction, the solution was neutralized with dilute hydrochloric acid; then, the neutralized solution was washed with a saturated sodium bicarbonate solution of the aqueous phase; then, the organic phase was removed, and the aqueous phase was extracted with ethyl acetate; then, the organic solutions were combined and distilled for the first time to reduce the volume; finally, the remaining material was purified by silica gel column chromatography, and finally the purified product was distilled again to finally obtain 99.5 g of colorless liquid (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethyl-2-(trifluoromethyl)acrylate with a yield of 83%.

[0053] Preparation Example 2 (Synthesis of 5-fluoronaphthalen-1-yl-2-(trifluoromethyl)acrylate represented by the following formula (7))

[0054]

[0055] The specific synthesis process is as follows:

[0056] 1) At 25 degrees Celsius and in a nitrogen atmosphere, 68.0 grams of oxalyl chloride were added dropwise to a solution containing 50.0 grams (386 millimoles) of trifluoromethylacrylic acid and 90 milliliters of dichloromethane, and finally a catalytic amount of N,N-dimethylformamide was added. The reaction mixture was heated to reflux at 50 degrees Celsius for 5 hours, and then the solvent and excess reagents were removed and concentrated using a rotary evaporator to obtain 2-trifluoromethylacryloyl chloride as a yellow liquid, which was directly used for the next step without purification.

[0057] 2) Add 45.0 g of 5-fluoronaphthalene-1-ol (CAS: 61761-32-8) to a 1000 ml three-necked round-bottom flask equipped with a magnetic stirrer and a constant pressure dropping funnel, and use a double-row tube to perform vacuum and nitrogen filling operations three times. Under a nitrogen atmosphere, add 500 ml of anhydrous dichloromethane and 27.0 g, 27.4 ml of pyridine, and then cool the reaction system to 0°C. Take the 2-trifluoromethylacryloyl chloride obtained in the previous step and add it to the constant pressure dropping funnel. Slowly add the mixed solution dropwise into the 0°C reaction system at a rate of 1 drop / second, and stir vigorously to ensure that the acyl chloride is promptly and fully dispersed. After the dropwise addition is completed, the mixture is stirred at room temperature overnight to react. After the reaction, the solution was neutralized with dilute hydrochloric acid; then, the neutralized solution was washed with a saturated sodium bicarbonate solution of the aqueous phase; then, the organic phase was removed, and the aqueous phase was extracted with ethyl acetate; then, the organic solutions were combined and distilled for the first time to reduce the volume; finally, the remaining material was purified by silica gel column chromatography, and the purified product was distilled again to finally obtain 70.5 g of colorless liquid 5-fluoronaphthalene-1-yl-2-(trifluoromethyl)acrylate with a yield of 89%.

[0058] Preparation Example 3 (Synthesis of perfluorobenzene 2-fluoroacrylate represented by the following formula (6))

[0059]

[0060] The specific synthesis process is as follows:

[0061] 1) At 0 degrees Celsius and in a nitrogen atmosphere, 105.7 grams of oxalyl chloride were added dropwise to a solution containing 50.0 grams (555 millimoles) of 2-fluoroacrylic acid and 90 milliliters of dichloromethane, and finally a catalytic amount of N,N-dimethylformamide was added. The reaction mixture was reacted at room temperature for 5 hours, and then the solvent and excess reagents were removed and concentrated using a rotary evaporator to obtain 2-fluoroacryloyl chloride as a yellow solid, which was directly used for the next step without purification.

[0062] 2) Add 65.0 g of perfluorobenzene-1-ol (CAS: 647-42-7) to a 1000 ml three-necked round-bottom flask equipped with a magnetic stirrer and a constant pressure dropping funnel, and use a double-row tube to perform vacuum and nitrogen filling operations three times. Under a nitrogen atmosphere, add 500 ml of anhydrous dichloromethane and 53.6 g, 54.6 ml of pyridine, and then cool the reaction system to 0°C. Take the 2-fluoroacryloyl chloride obtained in the previous step and add it to the constant pressure dropping funnel. Slowly add the mixed solution dropwise into the 0°C reaction system at a rate of 1 drop / second, and stir vigorously to ensure that the acid chloride is dispersed in time and fully. After the dropwise addition is completed, the mixture is stirred at room temperature overnight to react. After the reaction, the solution was neutralized with dilute hydrochloric acid; then, the neutralized solution was washed with a saturated sodium bicarbonate solution of the aqueous phase; then the organic phase was removed, and the aqueous phase was extracted with ethyl acetate; then, the organic solutions were combined and distilled for the first time to reduce the volume; finally, the remaining material was purified by silica gel column chromatography, and the purified product was distilled again to finally obtain 85.5 g of colorless liquid perfluorobenzene 2-fluoroacrylate with a yield of 94%.

[0063] Example 1

[0064] The encapsulation ink composition provided in an embodiment of the present invention comprises, by weight, 35 parts of a fluorinated aromatic compound, 30 parts of an ultraviolet light-curable monomer and 2 parts of a photocross-linking initiator; wherein the ultraviolet light-curable monomer is a mixture, comprising 20 parts of a (meth)acrylate containing a long carbon chain and 10 parts of a bridged ring photocurable monomer.

[0065] Specifically, the fluoroaryl compound is selected from the formula (1) synthesized by Preparation 1.

[0066] The (meth)acrylate containing a long carbon chain is selected from 1,6-hexanediol diacrylate.

[0067] The bridge ring photocurable monomer is isobornyl acrylate.

[0068] TPO was selected as the photocrosslinking initiator.

[0069] When preparing the ink composition, 35 parts of formula (1), 20 parts of 1,6-hexanediol diacrylate, 10 parts of isobornyl acrylate and 2 parts of TPO are mixed and stirred at room temperature in a light-proof environment until the initiator is completely dissolved, and the target ink composition is obtained after standing.

[0070] Example 2

[0071] The encapsulation ink composition provided in an embodiment of the present invention comprises, by weight, 20 parts of a fluorinated aromatic compound, 40 parts of an ultraviolet light-curable monomer, and 5 parts of a photocross-linking initiator; wherein the ultraviolet light-curable monomer is a mixture, comprising 25 parts of a (meth)acrylate containing a long carbon chain and 15 parts of a bridged ring photocurable monomer.

[0072] Specifically, the fluoroaryl compound is selected from the formula (1) synthesized by Preparation 1.

[0073] The (meth)acrylate containing a long carbon chain is selected from 2-methyl-2-acrylic acid-1,9-nonanediol dimethacrylate.

[0074] The bridge ring photocurable monomer is dicyclopentane methacrylate.

[0075] TPO was selected as the photocrosslinking initiator.

[0076] When preparing the ink composition, 20 parts of formula (1), 25 parts of 2-methyl-2-acrylic acid-1,9-nonanediol dimethacrylate, 15 parts of dicyclopentane methacrylate and 5 parts of TPO are mixed and stirred at room temperature in a light-proof environment until the initiator is completely dissolved, and the target ink composition is obtained after standing.

[0077] Example 3

[0078] The encapsulation ink composition provided in an embodiment of the present invention comprises raw materials, by mass, including 20 parts of fluorinated aromatic compounds, 60 parts of ultraviolet light-curable monomers and 5 parts of photocross-linking initiators; wherein the ultraviolet light-curable monomers are a mixture, including 30 parts of (meth)acrylates containing long carbon chains and 30 parts of bridged ring photocurable monomers.

[0079] Specifically, the fluoroaryl compound is selected from the formula (7) synthesized in Preparation 2.

[0080] The (meth)acrylate containing a long carbon chain is selected from 1,12-dodecanediol di(meth)acrylate.

[0081] The bridged ring photocurable monomer is dicyclopentenyl acrylate.

[0082] The photocrosslinking initiator is hydroxybenzophenone.

[0083] When preparing the ink composition, 20 parts of formula (7), 30 parts of 1,12-dodecanediol di(methyl)acrylate, 30 parts of dicyclopentenyl acrylate and 5 parts of hydroxybenzophenone are mixed and stirred at room temperature in a light-proof environment until the initiator is completely dissolved, and the target ink composition is obtained after standing.

[0084] Example 4

[0085] The encapsulation ink composition provided in an embodiment of the present invention comprises, by weight, 25 parts of a fluorinated aromatic compound, 65 parts of an ultraviolet light-curable monomer, and 4 parts of a photocross-linking initiator; wherein the ultraviolet light-curable monomer is a mixture, comprising 45 parts of a (meth)acrylate containing a long carbon chain and 20 parts of a bridged ring photocurable monomer.

[0086] Specifically, the fluoroaryl compound is selected from the formula (7) synthesized in Preparation 2.

[0087] The (meth)acrylate containing a long carbon chain is selected from 1,11-undecanediol dimethacrylate.

[0088] The bridged ring photocurable monomer is dicyclopentenyl acrylate.

[0089] The photocrosslinking initiator is hydroxybenzophenone.

[0090] When preparing the ink composition, 25 parts of formula (7), 45 parts of 1,11-undecanediol dimethacrylate, 20 parts of dicyclopentenyl acrylate and 4 parts of hydroxybenzophenone are mixed and stirred at room temperature in a light-proof environment until the initiator is completely dissolved, and the target ink composition is obtained after standing.

[0091] Example 5

[0092] The encapsulation ink composition provided in an embodiment of the present invention comprises, by weight, 22 parts of fluorinated aromatic compounds, 65 parts of ultraviolet light-curable monomers and 4 parts of photocross-linking initiators; wherein the ultraviolet light-curable monomers are a mixture, comprising 35 parts of (meth)acrylates containing long carbon chains and 30 parts of bridged ring photocurable monomers.

[0093] Specifically, the fluoroaryl compound is selected from the formula (6) synthesized by Preparation 3.

[0094] The (meth)acrylate containing a long carbon chain is selected from 1,5-pentanediol dimethacrylate.

[0095] The bridge ring photocurable monomer is cyclohexyl methacrylate.

[0096] The photo cross-linking initiator selected was 819.

[0097] When preparing the ink composition, 22 parts of formula (6), 35 parts of 1,5-pentanediol dimethacrylate, 30 parts of cyclohexyl methacrylate and 4 parts of 819 are mixed and stirred at room temperature in a light-proof environment until the initiator is completely dissolved, and the target ink composition is obtained after standing.

[0098] Example 6

[0099] The encapsulation ink composition provided in an embodiment of the present invention comprises, by weight, 30 parts of a fluorinated aromatic compound, 48 parts of an ultraviolet light-curable monomer and 3 parts of a photocross-linking initiator; wherein the ultraviolet light-curable monomer is a mixture, comprising 23 parts of a (meth)acrylate containing a long carbon chain and 25 parts of a bridged ring photocurable monomer.

[0100] Specifically, the fluoroaryl compound is selected from the formula (6) synthesized by Preparation 3.

[0101] The (meth)acrylate containing a long carbon chain is selected from 1,14-tetradecanediol di(meth)acrylate.

[0102] The bridge ring photocurable monomer is dicyclopentenyl ethoxylated acrylate.

[0103] The photo cross-linking initiator selected is 819.

[0104] When preparing the ink composition, 30 parts of formula (6), 23 parts of 1,14-tetradecanediol di(methyl)acrylate, 25 parts of dicyclopentenyl ethoxylated acrylate and 3 parts of 819 are mixed and stirred at room temperature in a light-proof environment until the initiator is completely dissolved, and the target ink composition is obtained after standing.

[0105] Comparative Example 1

[0106] The only difference between this comparative example and Example 1 is that no fluorinated aromatic compound of any structure is added to the ink composition of this comparative example.

[0107] Comparative Example 2

[0108] The only difference between this comparative example and Example 1 is that the amount of the compound of formula (1) added in this comparative example is 55 parts, that is, the amount of the fluorinated aromatic compound added in the ink composition of this comparative example is too much.

[0109] Comparative Example 3

[0110] The only difference between this comparative example and Example 1 is that in this comparative example, 20 parts of butyl methacrylate and 10 parts of isobornyl acrylate are selected as the UV-curable monomers, that is, the comparative example ink composition does not contain (meth)acrylates containing long carbon chains.

[0111] Comparative Example 4

[0112] The only difference between this comparative example and Example 1 is that in this comparative example, 20 parts of 1,6-hexanediol diacrylate and 10 parts of dodecafluoroheptyl methacrylate are added as UV-curable monomers, that is, the comparative example ink composition does not add bridged ring photocurable monomers.

[0113] Comparative Example 5

[0114] The only difference between this comparative example and Example 2 is that in this comparative example, 6 parts of 2-methyl-2-acrylic acid-1,9-nonanediol dimethacrylate and 30 parts of dicyclopentane methacrylate are selected as the UV-curable monomers, that is, the mass ratio of the long carbon chain (meth)acrylate to the bridge ring photocurable monomer in the ink composition of this comparative example is 6:30, which is not within the ratio range of (20-45): (10-30).

[0115] Table 1 Raw material ratios of Examples 1 to 6 and Comparative Examples 1 to 5

[0116]

[0117]

[0118] In order to verify the efficacy of the present invention, the applicant used 30 mW / cm 2 The film was cured by irradiation with UV light for 600s, and a 30μm thick cured film was obtained for performance testing. The specific aspects include the following:

[0119] (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.

[0120] (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.

[0121] (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.

[0122] (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).

[0123] (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.

[0124] (6) Photocuring rate: The encapsulation ink composition was inkjet printed on a glass substrate and subjected to a photocuring reaction at 30 mW / cm 2 The 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).

[0125] Photocuring rate (%) = |1-(F / S)| × 100;

[0126] 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

[0127] (7) Dielectric constant: The dielectric constant of the composition was tested at 10 GHz using GB / T 1693-2007.

[0128] (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.

[0129] (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.

[0130] (10) Bending resistance: An organic film of 2 cm × 5 cm × 3 μm (width × length × thickness) was formed on the surface of the PI substrate. The sample was prepared according to the method of forming the curing pattern except that the mask was not used. The short sides of the sample were fixed with tape. The sample was installed in a tensionless U-shaped folding tester (instrument name DLDMLH-FS, manufactured by Yuasa System Co., Ltd.). The outer diameter (Φ) of the bending part of the tester was set to 4 mm and the radius (R) was set to 2 mm. The sample was folded in half and subjected to a 180° dynamic bending test 200,000 times. The <Evaluation Criteria> are as follows: If the bending part does not have cracks or fractures, it is evaluated as (○); if the bending part has cracks or fractures, it is evaluated as (×).

[0131] The final test results are shown in Table 2 below:

[0132] Table 2 Test results of Examples 1 to 6 and Comparative Examples 1 to 5

[0133]

[0134] It can be seen from the test results in Table 2 that the ink compositions prepared by specific proportions of fluorinated aromatic compounds, ultraviolet light-curable monomers and photocrosslinking initiators in Examples 1 to 6 of the present invention have excellent comprehensive performance. Its viscosity and surface tension reach a range more suitable for inkjet printing, with high curing rate, high light transmittance and high refractive index, and the dielectric constant is significantly reduced, all of which can reach below 2.6, and the dielectric loss value is also reduced accordingly. At the same time, the combination of (meth) acrylates containing long carbon chains and bridge-ring photocurable monomers increases the crosslinking density, thereby improving heat resistance, with a Tg temperature of 80°C to 90°C, and has excellent flexibility, manifested as moderate tensile strength and elongation at break. In addition, the composition also has excellent bending resistance.

[0135] However, the test results of Comparative Example 1 show that if no fluorinated aromatic compound is added to the raw material, the dielectric reduction effect cannot be achieved; the test results of Comparative Example 2 show that when the amount of fluorinated aromatic compound added is too much, the dielectric constant is difficult to further reduce, and the sample tension and viscosity are too small to meet the printing requirements, and the glass transition temperature and tensile strength are also reduced; the test results of Comparative Example 3 show that the use of short carbon chain (meth) acrylates reduces the curing rate of the obtained organic barrier layer photocurable adhesive, and the surface tension and viscosity are not within the appropriate range, which is not suitable for inkjet printing, and the bending part will produce cracks or cracks; in Comparative Example 4, the bridge-type photocurable monomer uses methacrylate dodecafluoroheptyl, and a printing ink with low dielectric properties cannot be obtained, and the viscosity is too small to meet the printing requirements; in Comparative Example 5, the mass ratio of the long carbon chain (meth) acrylate to the bridge-type photocurable monomer is 1:5, which is not within the ratio range given in the present invention, and a printing ink with low dielectric properties cannot be obtained, and the bending resistance is poor and does not meet the requirements.

[0136] In summary, the ink composition provided by the present invention based on fluorinated aromatic compounds has many advantages, and the fluorinated curable monomer is cheap and easy to obtain, the preparation method is simple and easy to operate, the prepared low dielectric constant ink has a fast curing speed, and the obtained film has good light transmittance and low dielectric constant, which are all beneficial for encapsulating and protecting electronic devices.

[0137] 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.

[0138] 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. A fluorinated aromatic compound, characterized in that: The structure of the fluorinated aromatic compound is shown in the following general formula (1): Wherein, PAHs in the general formula (1) represents polycyclic aromatic hydrocarbons, which refers to substituted or unsubstituted aromatic hydrocarbons containing two or more benzene rings, and at least one group on each aromatic hydrocarbon is substituted by L or Z; the L and Z are each independently selected from any one of H, F, CFH2, CF2H, CF3, C1-C12 fatty chain alkyl, C1-C12 fluoroalkyl and the groups shown in the following general formula (2), and at least one group among L and Z is a fluorine-containing group, and the fluorine-containing group is any one of F, CFH2, CF2H, CF3, C1-C12 fluoroalkyl and the groups shown in the following general formula (2); In the general formula (1) and the general formula (2), X is independently selected from one of F and CF3, Y is selected from one of -ORO- and -NHRO-, and R in the -ORO- or -NHRO- is selected from one of C0-C12 substituted or unsubstituted aliphatic chain alkyl, C3-C6 substituted or unsubstituted aliphatic cycloalkyl, and C6-C30 substituted or unsubstituted aryl.

2. The fluorinated aromatic compound according to claim 1, characterized in that The structure of the fluorinated aromatic compound includes at least one of the following formulas (1) to (10):

3. A method for preparing a fluoroaryl compound according to claim 1 or 2, characterized in that: Under the protection of inert gas, a fluoroacrylic acid raw material, an acyl chloride raw material, a solvent and a catalyst are first mixed to obtain a fluoroacryloyl chloride product after reaction; then, the fluoroacryloyl chloride product is added to a mixed solution of an alcohol or phenol raw material containing fluorine atoms and an organic base, and after reaction and subsequent treatment, the fluoroaryl compound according to claim 1 or 2 is obtained.

4. The method for preparing a fluorinated aromatic compound according to claim 3, characterized in that: The molar ratio of the fluoroacrylic acid raw material to the acyl chloride raw material is 1:(2-4); The molar ratio of the alcohol or phenol raw material containing fluorine atoms to the fluoroacryloyl chloride product is 1:(2-4).

5. The method for preparing a fluorinated aromatic compound according to claim 3, characterized in that: The fluoroacrylic acid raw material includes trifluoromethylacrylic acid or 2-fluoroacrylic acid; The acyl chloride raw material includes oxalyl chloride; The alcohol or phenol raw material containing fluorine atoms includes (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethanol, 5-fluoronaphthalene-1-ol or perfluorobenzene-1-ol.

6. The method for preparing a fluorinated aromatic compound according to claim 3, characterized in that: The subsequent treatment process is as follows: after the reaction is completed, the solution is neutralized with dilute hydrochloric acid; then, the neutralized solution is washed with a saturated sodium bicarbonate solution of the aqueous phase; then the organic phase is removed, and the aqueous phase is extracted with ethyl acetate; then, the organic solutions are combined and distilled for the first time to reduce the volume; finally, the remaining substance is purified by silica gel column chromatography, and finally the purified product is distilled again.

7. An ink composition for packaging, characterized in that The invention comprises the following raw materials in parts by mass: 10 to 70 parts of an ultraviolet light-curable monomer, 1 to 10 parts of a photocrosslinking initiator and 5 to 50 parts of a fluoroaryl compound, wherein the fluoroaryl compound is the fluoroaryl compound according to claim 1 or 2, or the fluoroaryl compound prepared by the preparation method according to any one of claims 3 to 6.

8. The encapsulation ink composition according to claim 7, characterized in that: The ultraviolet light curable monomer is a mixture of a (meth)acrylate containing a long carbon chain and a bridge-ring photocurable monomer, and the mass ratio of the (meth)acrylate containing a long carbon chain to the bridge-ring photocurable monomer is (20-45): (10-30).

9. A method for using the encapsulation ink composition according to claim 7 or 8, characterized in that: The specific steps include: Step 1) firstly attaching the ink composition to the surface of the electronic device to be packaged by spin coating, doctor blade coating, screen printing or inkjet printing; Step 2: irradiate the ink composition with ultraviolet light having a wavelength of 250 nm to 400 nm for 30 s to 600 s, and finally solidify the ink composition to form an organic film having a thickness of 5 μm to 55 μm.

10. Use of the encapsulation ink composition according to claim 7 or 8 in preparing an organic barrier film for waterproofing and oxygen-blocking electronic components.

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