Patent Grant
11377570
This application is a national phase entry under 35 U.S.C. § 371 of International Application No. PCT/KR2019/010789 filed Aug. 23, 2019, which claims priority from Korean Patent Application No. 10-2018-0103831 filed Aug. 31, 2018, all of which are incorporated herein by reference.
The present invention relates to an ink composition for an organic light emitting device that can be applied to an inkjet process.
In general, an organic light emitting phenomenon refers to a phenomenon where electric energy is converted into light energy by using an organic material. The organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, an excellent contrast, a fast response time, an excellent luminance, driving voltage and response speed, and thus many studies have proceeded.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer frequently has a multilayered structure that includes different materials in order to enhance efficiency and stability of the organic light emitting device, and for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, the holes are injected from an anode into the organic material layer and the electrons are injected from the cathode into the organic material layer, and when the injected holes and electrons meet each other, an exciton is formed, and light is emitted when the exciton falls to a ground state again.
Meanwhile, recently, in order to reduce process costs, an organic light emitting device using a solution process, particularly an inkjet process, has been developed instead of a conventional deposition process. In the initial stage of development, attempts have been made to develop organic light emitting devices by coating all organic light emitting device layers by a solution process, but current technology has limitations. Therefore, only HIL, HTL, and EML are processed in a layer device structure by a solution process, and a hybrid process utilizing traditional deposition processes is being studied as a subsequent process.
Since the ink composition used in the inkjet process should have good discharge characteristics, it is necessary to use a solvent having a high boiling point. When using a solvent having a low boiling point, a nozzle part of an inkjet head may be clogged and there is a possibility that initial jetting properties are not good or meandering occurs. In addition, when the ink is filled and dried in a bank, which is a space where the ink composition is discharged, the ink film should be flatly filled in the bank without any step and the ink film surface should be smooth. However, when the solubility of a material in a solvent is poor, or when the material and the solvent do not match each other, in the process where the solvent is quickly dried (e.g., vacuum dried), precipitation occurs or surface characteristics (film image) are deteriorated. In order to solve the above problems, a solvent to be used must be appropriately selected according to the functional material contained in the ink composition. It is often difficult to solve both the film image and the film flatness only by selecting a solvent.
Therefore, in the present invention, the above problems are solved by using an additional additive in addition to the functional material and the solvent, as described below.
(Patent Literature 0001) Korean Patent Laid-open Publication No. 10-2000-0051826
It is an object of the present invention to provide an ink composition for an organic light emitting device that can be applied to an inkjet process.
In order to achieve the above object, one embodiment of the present invention provides an ink composition for an organic light emitting device including a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, and a solvent
in Chemical Formula 1,
L and L1 to L4 are each independently a substituted or unsubstituted C6-60 arylene,
Ar1 and Ar2 are each independently a substituted or unsubstituted C6-60 aryl; or a substituted or unsubstituted C2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
R1 to R4 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-60 alkyl, a substituted or unsubstituted C1-60 alkoxy, a substituted or unsubstituted C6-60 aryl, or a substituted or unsubstituted C2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
Y1 to Y4 are each independently hydrogen, or —X-A, with the proviso that two or more of Y1 to Y4 are —X-A,
X is O or S,
A is a functional group which can be crosslinked by heat or light,
n1 and n4 are each an integer of 0 to 4,
n2 and n3 are each an integer of 0 to 3,
in Chemical Formula 2,
R is C3-60 alkyl; C3-60 alkenyl; or phenyl substituted with C3-60 alkyl, and
n is an integer of 4 to 20.
The ink composition for forming an organic light emitting device according to the present invention can form a film having smooth and flat surfaces, when dried after forming an ink film by an inkjet process.
Hereinafter, embodiments of the present invention will be described in more detail to facilitate understanding of the invention.
As used herein, the notation
means a bond linked to another substituent group.
As used herein, the term “unsubstituted or substituted” means being unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylamine group; an arylphosphine group; or a heterocyclic group containing at least one of N, O and S atoms, or being unsubstituted or substituted with a substituent to which two or more substituents are linked among the substituents exemplified above. For example, “the substituent to which two or more substituents are linked” may be a biphenyl group. That is, the biphenyl group may also be an aryl group and may be interpreted as a substituent to which two phenyl groups are linked.
In the present specification, the number of carbon atoms of a carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structural formulas, but is not limited thereto.
In the present specification, an ester group may have a structure in which oxygen of the ester group may be substituted by a straight-chain, branched-chain, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a compound having the following structural formulas, but is not limited thereto.
In the present specification, the number of carbon atoms of an imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structural formulas, but is not limited thereto.
In the present specification, a silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group and the like, but is not limited thereto.
In the present specification, a boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group, but is not limited thereto.
In the present specification, examples of a halogen group include fluorine, chlorine, bromine, or iodine.
In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
In the present specification, the alkenyl group may be straight-chain or branched-chain, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to still another embodiment, the number of carbon atoms of the alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, a stilbenyl group, a styrenyl group, and the like, but are not limited thereto.
In the present specification, a cycloalkyl group is not particularly limited, but the number of carbon atoms thereof is preferably 3 to 60. According to one embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to still another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
In the present specification, an aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group or the like, but is not limited thereto.
In the present specification, a fluorenyl group may be substituted, and two substituent groups may be connected with each other to form a spiro structure. In the case where the fluorenyl group is substituted,
and the like can be formed. However, the structure is not limited thereto.
In the present specification, a heterocyclic group is a heterocyclic group including one or more of O, N, Si and S as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazol group, an oxadiazol group, a triazol group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group, a pyridazine group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazol group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but are not limited thereto.
In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the aforementioned examples of the aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group and the alkylamine group is the same as the aforementioned examples of the alkyl group. In the present specification, the heteroaryl in the heteroarylamine can be applied to the aforementioned description of the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the aforementioned examples of the alkenyl group. In the present specification, the aforementioned description of the aryl group may be applied except that the arylene is a divalent group. In the present specification, the aforementioned description of the heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the aforementioned description of the aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group but formed by combining two substituent groups. In the present specification, the aforementioned description of the heterocyclic group can be applied, except that the heterocycle is not a monovalent group but formed by combining two substituent groups.
Compound Represented by Chemical Formula 1
The compound represented by Chemical Formula 1 is a material constituting a functional layer in the organic light emitting device. By including oxygen (O) or sulfur (S) atoms in the compound, it is possible to form a stable thin-film completely cured by heat treatment or UV treatment. In addition, it has high affinity with solvents and thus has solvent selectivity (orthogonality). Moreover, it has a resistance to the solvent used when forming another layer by a solution process, in addition to the organic material layer containing the above compound, and thus can prevent movement to another layer. In addition, the the organic light emitting device including the same can have low driving voltage, high light emitting efficiency and high lifetime characteristics.
Preferably, A is any one selected from the group consisting of the following:
wherein,
T1 is hydrogen or a substituted or unsubstituted C1-60 alkyl, and
T2 to T4 are each independently a substituted or unsubstituted C1-6 alkyl.
Preferably, the Chemical Formula 1 is represented by any one of the following Formulas 1-1 to 1-4:
in Chemical Formulas 1-1 to 1-4,
R1 to R4, n1 to n4, Ar1, Ar2 and L are as previously defined in Chemical Formula 1,
X1 to X4 are each independently O or S,
A1 to A4 are each independently a functional group that can be crosslinked by heat or light,
R21 to R26 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-60 alkyl, a substituted or unsubstituted C1-60 alkoxy, a substituted or unsubstituted C6-60 aryl, or a substituted or unsubstituted C2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S, and
p1 and p2 are each an integer of 0 to 5,
p3 and p4 are each an integer of 0 to 4,
p5 and p6 are each an integer of 0 to 7.
Preferably, L is the following Chemical Formula 1-A or 1-B:
in Chemical Formulas 1-A and 1-B,
R11 to R13 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-60 alkyl, a substituted or unsubstituted C1-60 alkoxy, a substituted or unsubstituted C6-60 aryl, or a substituted or unsubstituted C2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S, and
m1 to m3 are each an integer of 0 to 4.
Representative examples of the compound represented by Chemical Formula 1 are as follows:
On the other hand, the compound represented by Chemical Formula 1 may be prepared by the preparation method as shown in the following Reaction Scheme 1.
In Reaction Scheme 1, the remaining definitions excluding X′ are as defined above, and X′ is halogen, preferably bromo, or chloro. Reaction Scheme 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactive group for the amine substitution reaction can be modified as known in the art. The above preparation method may be further specified in Preparation Examples described hereinafter.
On the other hand, the coating composition according to the present invention further includes a p-type doping material in addition to the compound represented by Chemical Formula 1. The p-type doping material refers to a material that enables a host material to have p-type semiconductor properties. The p-type semiconductor properties refer to properties such that holes are injected or transported through the highest occupied molecular orbital (HOMO) energy level, that is, properties of a material having high hole conductivity.
Preferably, the p-type doping material may be represented by any one of the following Chemical Formulas A to H.
Preferably, the content of the p-type doping material is 0% by weight to 50% by weight relative to the compound represented by Chemical Formula 1.
Compound Represented by Chemical Formula 2
A functional layer may be formed by a solution process using the compound represented by Chemical Formula 1, but recently, among the solution process, an inkjet printing process is most frequently studied. Since the inkjet printing process discharges fine drops, there is an advantage that not only the consumption of materials can be minimized but also precise patterns are possible.
In the inkjet process, the ink is discharged to pixel parts and then the solvent is dried to form an intended functional layer. In this process, it is difficult to form a flat film (excellent in film flatness) with a few steps in pixels while having a smooth surface (excellent in film image). In other words, some inks have excellent film flatness, such as showing a few steps in pixels, but large film surface roughness may show or problems such as precipitation may occur, and thus, poor film image may show. On the contrary, the film image is excellent, but a film flatness may appear poor, for example, the ink film climbs up a bank wall or the center of the pixel is convex. In other words, it is often very difficult to find a solvent that satisfies both conditions.
However, the present invention further includes a compound represented by Chemical Formula 2 so that the above-described problem does not occur even when the compound represented by Chemical Formula 1 is applied to the inkjet process.
Although not limited by a specific theory, the compound represented by Chemical Formula 2 has a hydrophilic group and a hydrophobic group at the same time, and thus, in the process of vacuum drying the compound represented by Chemical Formula 1, it adjusts an interaction between the solvent and the material so that a flat layer is formed after drying.
Preferably, R is C10-20 alkyl; C10-20 alkenyl; or phenyl substituted with C10-20 alkyl.
The compound represented by Chemical Formula 2 may be prepared directly or purchased commercially, and representative examples include Brij® C10, Brij® S10, Brij® 010, IGEPAL® CO-520, IGEPAL® CO-630, Triton® X-100, Triton® X-114, Triton® X-45 and the like.
On the other hand, the compound represented by Chemical Formula 2 is preferably included in an amount of 0.05 to 1% by weight relative to the total weight of the ink composition according to the present invention. When the content is less than 0.05% by weight, the effect due to the addition of the compound represented by Chemical Formula 2 is insignificant, and when the content exceeds 1% by weight, not only the effect due to the addition is not substantially increased, but also rather, there is a risk of hindering the luminous efficiency and lifetime of the organic light emitting device.
Solvent
The solvent used in the present invention is a solvent that dissolves the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 and that is used in an inkjet process. In addition, when the p-type doping material mentioned above is used, it is a solvent that can dissolve this material together.
Since the inkjet process discharges fine droplets of ink via an inkjet head, the discharge stability at the head (straightness, no non-discharge, good initial jetting properties, etc.) is important. Thus, it is important to maintain so that the solution is not dried at a nozzle portion. When the ink is dried at the nozzle portion, problems such as nozzles being clogged and ink being discharged into a crooked or zigzag shape (meandering) may occur, but in order to prevent these problems, a solvent having a high boiling point is generally used.
The solvent has a boiling point of preferably 180° C. or more, more preferably 190° C. or more, and most preferably 200° C. or more. On the other hand, the upper limit of the boiling point is not particularly limited. However, when the boiling point is too high, it is difficult to dry the solvent. Thus, for example, the boiling point is 400° C. or lower, preferably 350° C. or lower.
The solvent may be used without limitation as long as it is a solvent having a high boiling point and can dissolve the material of the functional layer well. It may be a single solvent or a mixed solvent composition. Among them, in the case of including the solvents below, the effect of the additive can be further maximized, and examples thereof include aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers, aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, aromatic alcohols, or glycol ethers.
Preferably, the solvent is represented by the following Chemical Formula 3:
in Chemical Formula 3,
R′ is hydrogen, C1-5 alkyl, or C6-60 aryl,
R″ is C1-10 alkyl, C1-10 alkoxy, hydroxy, or —COO— (C1-10 alkyl), and n is an integer of 1 to 6.
The compound represented by Chemical Formula 3 is a glycol ether-based solvent and has low surface tension, which is advantageous for forming a flat layer.
Typical examples of the solvent include triethylene glycol monobutyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol n-butyl ether, triethylene glycol monoisopropyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoisobutyl ether, dipropylene glycol n-butyl ether and the like.
In addition, there may be mentioned 3-pheoxytoluene, dibenzyl ether, bis(methoxymethyl)benzene, isoamylbenzoate, isoamyl octanoate, decylbenzene, 1-methoxynaphthalene, phenethyl octanoate, 1,3-dimethoxybenzene, ethyl 4-methoxybenzoate, hexyl benzoate, 1-ethylnaphthalene, cyclohexylbenzene, octylbenzene, 2-ethylnaphthalene, benzyl butyrate, p-anisaldehyde dimethyl acetal, 3-phenyl-1-propanol, p-propylanisole, ethyl benzoate, butyl phenyl ether, 3,4-dimethylanisole, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, dibutyl oxalate, 3-phenoxybenzyl alcohol and the like.
Ink Composition
The ink composition according to the present invention described above can be used for the preparation of a functional layer of an organic light emitting device. The ink composition may be used to prepare a functional layer of an organic light emitting device by a solution process, and in particular, it may be applied to an inkjet process.
The inkjet process may use a method used in the art, except for using the ink composition according to the present invention described above. As an example, the process may include a step of discharging the ink composition to form an ink film; and a step of drying the ink film. Moreover, since the compound represented by Chemical Formula 1 includes a functional group that can be crosslinked by heat or light, it may further include a step of performing heat treatment or light treatment after the above steps.
Meanwhile, the functional layer which may be formed of the ink composition may be a hole injection layer, a hole control (transport) layer and a light emitting layer of the organic light emitting device. Moreover, since the structure and manufacturing method of the organic light emitting device used in the art can be applied except for the functional layer, a detailed description will be omitted herein.
Hereinafter, preferred examples are provided to facilitate understanding of the present invention. However, the following examples are merely provided for a better understanding of the present invention, and the scope of the present invention is not limited thereby.
1) Preparation of Intermediate 1-1
2-Bromo-9-phenyl-9H-fluorene-9-ol (50 g, 148.3 mmol, 1.0 eq) and phenol (41.8 g, 444.9 mmol, 3.0 eq) were added to a 500-ml round flask and dissolved in methanesulfonic acid (200 ml, 0.74 M). The mixture was stirred at reflux overnight. Subsequently, the reaction was stopped with a saturated NaHCO3 aqueous solution, and then the organic layer was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then the solvent was removed and purified by column chromatography to obtain Intermediate Compound 1-1.
2) Preparation of Intermediate 1-2
Intermediate 1-1 (30 g, 63.9 mmol, 1.0 eq) and cesium carbonate (41.6 g, 127.8 mmol, 2.0 eq) were dissolved in DMF (120 ml, 0.5 M) in a 500-ml round flask and then heated to 50° C. and stirred. Then, 4-vinylbenzyl chloride (9.15 ml, 9.75 g, 1.0 eq) was added thereto and stirred at 60° C. After cooling to room temperature, water was added to stop the reaction. The organic layer was then extracted using ethyl acetate. The organic layer was separated, dried over magnesium sulfate, and the solvent was removed and purified by column chromatography to obtain Intermediate Compound 1-2.
3) Preparation of Compound 1
Intermediate 1-2 (12.0 g, 20.49 mmol, 2.05 eq), N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (3.36 g, 10.0 mmol, 1.0 eq), NaOtBu (3.36 g, 34.99 mmol, 3.5 eq), and Pd(PtBu3)2 (255 mg, 0.5 mmol, 0.05 eq) were dissolved in toluene (100 ml) in a 250-ml round flask, then stirred and reacted under a nitrogen atmosphere. Subsequently, after completion of the reaction, it was worked-up with water and ethyl acetate, and the organic layer was separated, dried and then filtered. Subsequently, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography and the solvent was removed to obtain Compound 1 (white solid).
1H NMR (500 MHz): δ 8.00-7.82 (m, 4H), 7.70-7.68 (d, 4H), 7.62-7.55 (m, 6H), 7.35-7.15 (m, 38H), 7.05-7.03 (t, 2H), 6.92-9.85 (d, 4H), 6.73-6.70 (m, 2H), 5.76-5.73 (d, 2H), 5.39-5.37 (d, 2H), 5.17 (s, 4H)
1) Preparation of Intermediate 2-1
4-(2-Bromo-9-(4-(tert-butyl)phenyl)-9H-fluoren-9-yl)phenol (50 g, 106.50 mmol, 1.0 eq), 4-bromobenzaldehyde (23.6 g, 127.8 mmol, 1.2 eq) and potassium carbonate (44.2 g, 319.50 mmol, 3.0 eq) were added to a 500-ml round flask and dissolved in dry pyridine (200 ml, 0.5 M). Then, copper(II) oxide (17.0 g, 213.0 mmol, 2 eq) was added slowly and heated to 120° C., and the reaction allowed to proceed under reflux. When the reaction was completed, the reaction was stopped with saturated aqueous NaHCO3 solution and the organic layer was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate to remove the solvent, and the resulting crude material was dissolved in dichloromethane and precipitated with ethanol to obtain Intermediate Compound 2-1 as a solid.
2) Preparation of Intermediate 2-2
Anhydrous tetrahydrofuran (50 ml, 0.2 M) was added to a round flask containing methyltriphenylphosphonium bromide (12.46 g, 34.87 mmol, 2.0 eq) and the round flask was immersed in an ice bath. Potassium tert-butoxide (3.9 g, 34.87 mmol, 2.0 eq) was added in one portion and stirred in an ice bath for 20 minutes. Intermediate compound 2-1 (10.0 g, 17.44 mmol, 1.0 eq) was dissolved in tetrahydrofuran (30 ml) and then gradually added to the mixture using a dropping funnel. Then, the round flask and the funnel were rinsed with tetrahydrofuran (10 ml) and put thereto. Water (50 ml) was added to terminate the reaction, and the organic layer was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate, and then the solvent was removed and purified by column chromatography to obtain Compound 2-2.
3) Preparation of Compound 2
Intermediate Compound 2-2 (10.0 g, 17.50 mmol, 2.05 eq), N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (2.87 g, 8.53 mmol, 1.0 eq), NaOtBu (2.87 g, 29.86 mmol, 3.5 eq) and Pd(PtBu3)2 (218.0 mg, 0.43 mmol, 0.05 eq) were dissolved in toluene (90 ml) in a 250-ml round flask, then stirred and reacted under a nitrogen atmosphere. Subsequently, after completion of the reaction, it was worked-up with water and ethyl acetate, and the organic layer was separated, dried and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography and the solvent was removed to obtain Compound 2 (white solid).
1H NMR (500 MHz): b 7.95-7.83 (m, 4H), 7.65-7.58 (m, 10H), 7.54-7.26 (m, 22H), 7.24-7.05 (m, 12H), 6.95-6.93 (d, 4H), 6.86-6.84 (d, 4H), 6.80-6.76 (m, 2H), 5.65-5.61 (d, 2H), 5.16-5.13 (d, 2H), 1.35 (s, 18H)
1) Preparation of Intermediate 3-1
4-(2-Bromo-9-(p-tolyl)-9H-fluoren-9-yl)phenol (15 g, 35.1 mmol, 1.0 eq), potassium carbonate (14.6 g, 105.3 mmol, 3 eq), copper(I) iodide (334.3 mg, 1.76 mmol, 0.05 eq) and 1-butylimidazole (4.4 g, 35.1 mmol, 1.0 eq) were added to a 250-ml round flask and dissolved in toluene (175 ml). After the reflux apparatus was installed, the mixture was heated to 120° C. and the reaction allowed to proceed under stirring. When the reaction was completed, the reaction was stopped with saturated aqueous NaHCO3 solution and worked up with water and ethyl acetate. The organic layer was separated, dried over MgSO4 and filtered. Subsequently, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography to obtain Compound 3-1.
2) Preparation of Compound 3
Intermediate Compound 3-1 (10.0 g, 18.89 mmol, 2.05 eq), N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (3.10 g, 9.21 mmol, 1.0 eq), NaOtBu (3.10 g, 32.24 mmol, 3.5 eq) and Pd(PtBu3)2 (235.1 mg, 0.46 mmol, 0.05 eq) were dissolved in toluene (120 ml) in a 250-ml round flask, then stirred and reacted under a nitrogen atmosphere. Subsequently, after completion of the reaction, it was worked-up with water and ethyl acetate, and the organic layer was separated, dried and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography and the solvent was removed to obtain Compound 3 (white solid).
1H NMR (500 MHz): δ 7.90-7.87 (m, 4H), 7.56-7.53 (m, 6H), 7.48-7.30 (m, 16H), 7.27 (s, 2H), 7.25-7.22 (d, 4H), 7.20-7.15 (m, 18H), 7.14-7.12 (d, 4H), 2.88 (s, 8H), 2.19 (s, 6H)
1) Preparation of Intermediate 4-1
4,4′-(2-Bromo-9H-fluorene-9,9-diyl)diphenol (10 g, 23.3 mmol, 1.0 eq), potassium carbonate (9.7 g, 69.9 mmol, 3 eq), copper(I) iodide (220.4 mg, 1.17 mmol, 0.05 eq) and 1-butylimidazole (2.9 g, 23.3 mmol, 1.0 eq) were added to a 250-ml round flask and dissolved in toluene (100 ml). After adding 3-bromobenzene (3.66 g, 23.3 mmol, 1.0 eq), a reflux apparatus was installed, which was heated to 120° C., and the reaction allowed to proceed under stirring. When the reaction was completed, the reaction was stopped with saturated aqueous NaHCO3 solution and worked up with water and ethyl acetate. The organic layer was separated, dried over MgSO4 and then filtered. Subsequently, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography to obtain Compound 4-1.
2) Preparation of Intermediate 4-2
Intermediate 4-1 (10 g, 19.78 mmol, 1.0 eq), potassium carbonate (8.20 g, 59.36 mmol, 3 eq), copper(I) iodide (187.1 mg, 0.99 mmol, 0.05 eq) and 1-butylimidazole (2.42 g, 19.78 mmol, 1.0 eq) were added to a 250-ml round flask and dissolved in toluene (100 ml). After adding 3-bromobicyclo[4.2.0]octa-1(6),2,4-triene (3.98 g, 21.75 mmol, 1.1 eq), a reflux apparatus was installed, which was heated to 120° C., and the reaction allowed to proceed under stirring. When the reaction was completed, the reaction was stopped with saturated aqueous NaHCO3 solution and worked up with water and ethyl acetate. The organic layer was separated, dried over MgSO4 and then filtered. The solvent was then removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography to obtain Compound 4-2.
3) Preparation of Compound 4
Intermediate Compound 4-2 (10.0 g, 16.46 mmol, 2.05 eq), N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (2.70 g, 8.03 mmol, 1.0 eq), NaOtBu (2.70 g, 28.10 mmol, 3.5 eq), and Pd(PtBu3)2 (205.2 mg, 0.40 mmol, 0.05 eq) were dissolved in toluene (90 ml) in a 250-ml round flask, then stirred and reacted under a nitrogen atmosphere. Subsequently, after completion of the reaction, it was worked-up with water and ethyl acetate, and the organic layer was separated, dried and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography and the solvent was removed to obtain Compound 4 (white solid).
1H NMR (500 MHz): δ 7.88-7.85 (m, 4H), 7.57-7.55 (m, 6H), 7.52-7.30 (m, 20H), 7.27-7.15 (m, 18H), 7.07-6.90 (m, 16H), 2.85 (s, 8H)
1) Preparation of Intermediate 5-1
2-Bromo-9H-fluoren-9-one (15 g, 57.9 mmol, 1.0 eq) and phenol (54.5 g, 579 mmol, 10.0 eq) were added to a 250-ml round flask and dissolved in methanesulfonic acid (70 ml, 0.8 M). The mixture was stirred at 60° C. overnight. Then, water was poured to terminate the reaction, and the resulting precipitate was washed with water and filtered. The obtained filtrate was dissolved in a small amount of ethyl acetate and dropped into hexane to proceed the precipitation process. Filtration yielded Intermediate Compound 5-1 as a white solid.
2) Preparation of Intermediate 5-2
Intermediate 5-1 (10 g, 23.29 mmol, 1.0 eq) and cesium carbonate (9.1 g, 27.95 mmol, 1.2 eq) were dissolved in dimethylformamide (50 ml, 0.47 M) in a 250-ml round flask, then heated to 100° C. and stirred. Then, 2-ethylhexyl bromide (3.71 ml, 20.96 mmol, 0.9 eq) was slowly added thereto and stirred. When the reaction was completed, the reaction mixture was cooled to room temperature, and water was added to stop the reaction. The organic layer was then extracted using ethyl acetate. The organic layer was separated, dried over magnesium sulfate, and then the solvent was removed and purified by column chromatography to obtain Intermediate Compound 5-2.
3) Preparation of Intermediate 5-3
Intermediate 5-2 (10 g, 15.5 mmol, 1.0 eq), potassium carbonate (6.4 g, 46.6 mmol, 3 eq), copper(I) iodide (147.6 mg, 0.78 mmol, 0.05 eq) and 1-butylimidazole (1.9 g, 15.5 mmol, 1.0 eq) were added to a 250-ml round flask and dissolved in toluene (77 ml). After the reflux apparatus was installed, the mixture was heated to 120° C. and the reaction allowed to proceed under stirring. When the reaction was completed, the reaction was stopped with saturated aqueous NaHCO3 solution and worked up with water and ethyl acetate. The organic layer was separated, dried over MgSO4 and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography to obtain Compound 5-3.
4) Preparation of Intermediate 5
Intermediate Compound 5-3 (10.0 g, 15.54 mmol, 2.05 eq), N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (2.55 g, 7.58 mmol, 1.0 eq), NaOtBu (2.55 g, 26.53 mmol, 3.5 eq) and Pd(PtBu3)2 (194 mg, 0.38 mmol, 0.05 eq) were dissolved in toluene (90 ml) in a 250-ml round flask, then stirred and reacted under a nitrogen atmosphere. Subsequently, after completion of the reaction, it was worked-up with water and ethyl acetate, and the organic layer was separated, dried and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography and the solvent was removed to obtain Compound 5 (white solid).
1H NMR (500 MHz): δ 7.90-7.85 (m, 4H), 7.55-7.52 (m, 6H), 7.48-7.26 (m, 22H), 7.24-7.05 (m, 10H), 6.95-6.93 (d, 4H), 6.86-6.84 (d, 4H), 3.98-3.97 (m, 2H), 3.73-3.70 (m, 2H), 2.90 (s, 8H), 1.70-1.67 (m, 2H), 1.55-1.52 (m, 4H), 1.32-1.25 (m, 12H), 0.95-0.92 (t, 6H), 0.90-0.88 (t, 6H)
1) Preparation of Intermediate 6-1
4-(2-Bromo-9-(4-((2-ethylhexyl)oxy)phenyl)-9H-fluoren-9-yl)phenol (15 g, 27.7 mmol, 1.0 eq) and potassium carbonate (11.5 g, 83.1 mmol, 3 eq) were added to a 250-ml round flask and dissolved in DMF (150 ml). 3-(Bromomethyl)-3-ethyloxetane (5.5 g, 30.5 mmol, 1.1 eq) was added thereto, and the mixture was heated at 70° C. and the reaction allowed to proceed under stirring. After completion of the reaction, it was worked-up with water and ethyl acetate. The organic layer was separated, dried over MgSO4 and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography to obtain Compound 6-1.
2) Preparation of Compound 6
Intermediate Compound 6-1 (10.0 g, 15.63 mmol, 2.05 eq), N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (2.56 g, 7.62 mmol, 1.0 eq), NaOtBu (2.56 g, 26.67 mmol, 3.5 eq) and Pd(PtBu3)2 (194.7 mg, 0.38 mmol, 0.05 eq) were dissolved in toluene (100 ml) in a 250-ml round flask, then stirred and reacted under a nitrogen atmosphere. Subsequently, after completion of the reaction, it was worked-up with water and ethyl acetate, and the organic layer was separated, dried and then filtered. Then, the solvent was removed with a rotary vacuum evaporator. The resulting crude material was purified by column chromatography and the solvent was removed to obtain Compound 6 (white solid).
1H NMR (500 MHz): δ 7.91-7.95 (m, 4H), 7.56-7.53 (m, 6H), 7.45-7.20 (m, 30H), 6.87-6.83 (m, 8H), 4.37-4.35 (d, 4H), 4.13-4.10 (d, 4H), 3.94-3.90 (m, 2H), 3.80 (s, 2H), 3.75-3.71 (m, 2H), 1.80-1.78 (m, 2H), 1.70-1.68 (q, 4H), 1.55-1.53 (m, 4H), 1.30-1.18 (m, 12H), 0.99-0.96 (t, 6H), 0.88-0.84 (m, 12H)
Compound 1 (1.6 wt %) prepared in Preparation Example 1 and the following Compound A (0.4 wt %) as a functional material, Triton X-45 (0.1 wt %) as an additive, and TEGBE (Triethylene glycol monobutyl ether; 97.9 wt %) as a solvent were mixed and stirred to prepare an ink composition.
An ink composition was prepared in the same manner as in Example 1, except that each component contained in the ink composition was used as shown in Tables 1 to 6 below. On the other hand, in Tables 1 to 6, each abbreviation of the solvents has the following meaning, and the compounds B and C are as follows.
TEGBE: Triethylene glycol monobutyl ether
6-MTN: 6-methoxytetrahydronaphthalene
DEGDBE: Diethylene glycol dibutyl ether
tetEGDME: tetraethylene glycol dimethyl ether
The properties of the ink compositions prepared in Examples and Comparative Examples were evaluated through the following experiments.
1) Solubility: In the ink compositions prepared in Examples and Comparative Examples, if the compounds of Chemical Formulas 1 to 6 was dissolved at 1.0 wt % or more, respectively, at room temperature (23° C.), they were evaluated as O.K, and if the compounds were dissolved at 0.5 wt % or less, they were evaluated as N.G.
2) Film image: The ink compositions prepared in Examples and Comparative Examples were injected into the head of a Dimatix Materials Cartridge (FUJIFILM), and ink droplets were discharged by nine drops on each pixel (see
3) Jetting properties: In the previous film image evaluation, when all nozzles were discharged without clogging for at least 5 minutes and the ink was discharged to have a straightness, it was evaluated as O.K, and if there was no discharge or the ink drop was ejected into a crooked or zigzag shape at the time of discharge, it was evaluated as N.G.
4) Film flatness: As shown in
The above results are shown in Tables 1 to 6 below.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0103831 | Aug 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2019/010789 | 8/23/2019 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/045904 | 3/5/2020 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20070029556 | Su | Feb 2007 | A1 |
| 20090033208 | Nagayama et al. | Feb 2009 | A1 |
| 20100323464 | Cheon et al. | Dec 2010 | A1 |
| 20120021547 | Kawanishi | Jan 2012 | A1 |
| 20140217379 | Humphries | Aug 2014 | A1 |
| 20160225480 | Kim | Aug 2016 | A1 |
| 20170213967 | Chen | Jul 2017 | A1 |
| 20170229656 | Zhu | Aug 2017 | A1 |
| 20180215998 | Hirayama | Aug 2018 | A1 |
| 20190237669 | Kang et al. | Aug 2019 | A1 |
| 20190305241 | Angioni | Oct 2019 | A1 |
| 20210151684 | Adachi | May 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 102293055 | Dec 2011 | CN |
| 107721805 | Feb 2018 | CN |
| 2010170829 | Aug 2010 | JP |
| 20000051826 | Aug 2000 | KR |
| 20110119716 | Nov 2011 | KR |
| 101108519 | Jan 2012 | KR |
| 101111413 | Feb 2012 | KR |
| 20120037409 | Apr 2012 | KR |
| 20120096075 | Aug 2012 | KR |
| 20150073721 | Jul 2015 | KR |
| 20150093995 | Aug 2015 | KR |
| 20180030644 | Mar 2018 | KR |
| 20180092270 | Aug 2018 | KR |
| 2013002514 | Jan 2013 | WO |
| Entry |
|---|
| International Search Report from Application No. PCT/KR2019/010789 dated Dec. 10, 2019, 2 pages. |
| Lopez et al., “Characterization of PEDOT:PSS dilutions for inkjet printing applied to OLED fabrication”, Proceedings of the 7th International Caribbean Conference on Devices, Circuits and Systems, IEEE, Mexico, Apr. 28-30, 2008, 4 pages. |
| Search Report for Chinese Application No. 201980006237.1 dated Dec. 1, 2021. 1 pg. |
| “Report on Advances in Chemistry”, (Apr. 2009). 3 pgs. |
| Number | Date | Country | |
|---|---|---|---|
| 20200308435 A1 | Oct 2020 | US |
