KR102065710B1 - Azide-type Crosslinking Agent Having Many Crosslinking Functional Groups - Google Patents

Abstract

The present invention relates to a photocrosslinking binder (crosslinking agent) having an azide group, and more particularly to a crosslinking agent effective in increasing photocrosslinking efficiency by increasing the number of crosslinking functional groups in preparing an azide type crosslinking agent.
According to various embodiments of the present invention, it is possible to provide a crosslinking agent having a high crosslinking efficiency while significantly reducing the amount of photocrosslinking initiator that may act as an impurity.
In addition, the crosslinking agent is excellent in the crosslinking efficiency in the solution process that is actively studied in the field of electronic devices, and can maintain sufficient solvent resistance, thereby showing an effect that can be applied to various device fields.

Description

Azide-type Crosslinking Agent Having Many Crosslinking Functional Groups

The present invention relates to a photocrosslinking binder (crosslinking agent) having an azide group, and more particularly to a crosslinking agent effective in increasing photocrosslinking efficiency by increasing the number of crosslinking functional groups in preparing an azide type crosslinking agent.

The research on the solution process of organic electronic materials is a field that is being studied because of the advantages that the material use efficiency and the equipment cost is low compared to the existing vacuum deposition process, which can lower the process cost of the product.

However, most organic electronic devices such as organic light emitting diodes (OLEDs), organic thin-film transistors (OTFTs), and solar cells use a multilayered film structure for high device driving efficiency and device driving stability. Although it can be said to be an advantageous process for forming the organic film multilayer structure, the solution process is difficult to apply the process because there is a problem, such as a lower film erosion to form a multilayer film structure. When the upper layer is formed on the already formed organic layer, the solvent used for the upper layer must dissolve the lower layer or penetrate the lower layer to damage the lower layer, so that the organic electronic material of the multilayer structure can be made using the solution process. have. As a solution to this problem, there is a method of increasing the resistance to solvent by crosslinking the lower layer using a thermal crosslinking or optical crosslinking using a crosslinking material, and in the case of optical crosslinking, a process time is relatively higher than that of thermal crosslinking. As it is short, there is an advantage in mass production process.

However, the photoinitiator used in photocrosslinking can act as an impurity in organic electronic materials, and devices using organic electronic materials can secure high solvent resistance even with a small amount because purity directly affects the stability of the device. Photoinitiator with high crosslinking efficiency should be used. In addition, the conventional azide crosslinking agent has a problem in that there is a limit in improving the crosslinking efficiency including up to two azide groups.

Accordingly, the present invention aims to provide a crosslinking agent capable of securing high solvent resistance even at a small concentration by introducing a larger number of crosslinking functional groups into the azide type photocrosslinker having the above-described advantages, thereby further improving crosslinking properties.

Korean Patent No. 1754044

An object of the present invention is to develop a new azide type photocrosslinking compound having high crosslinking efficiency in solution process, which is currently being actively studied in the field of electronic devices, thereby reducing the amount of photocrosslinking initiator that can act as an impurity in solution process. An object of the present invention is to provide a crosslinking agent capable of maintaining sufficient solvent resistance.

According to an exemplary aspect of the present invention, it relates to a crosslinking agent represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

A, R ₁ and R ₂ are the same as or different from each other, and are each independently selected from a hydrogen atom, a halogen group, a C1 to C10 straight or branched chain alkyl group and an azide group,

이며,R ₅ and R ₆ are the same as or different from each other, and each independently a valence bond, a hydrogen atom, or

Is,

R ₃ and R ₃ ′ are the same as or different from each other, and are each independently selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,

R ₄ and R ₄ ′ are the same as or different from each other, and each independently a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- R ₉ -is selected from

R ₇ , R ₈ and R ₉ are the same as or different from each other, and each independently, a valence bond, a C1 to C10 straight or branched chain alkyl group, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thio s Selected from the

Z is a valence bond, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C5 to C20 aryl group, Substituted or unsubstituted C5 to C20 heteroaryl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C6 to C20 arylamine group, substituted or unsubstituted C1 to C20 heteroarylamine group, substituted Or an unsubstituted C1 to C20 alkylsilyl group, a substituted or unsubstituted C6 to C20 arylsilyl group, or a substituted or unsubstituted C5 to C20 heteroarylsilyl group,

N = an integer of 3 to 6, m = an integer of 1 to 2, x = an integer of 1 to 3.

The crosslinking agent represented by Chemical Formula 1 is preferably represented by any one of the following Chemical Formulas 2 to 5.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,

이고,Y is

ego,

R ₁ is a hydrogen atom or an azide group,

A is a hydrogen atom or a halogen group,

R ₂ is a hydrogen atom or a C1 to C6 linear or branched alkyl group,

R ₃ is selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,

R ₄ is selected from a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- ,

R ₇ and R ₈ are the same as or different from each other, and are each independently selected from a valence bond, C1 to C10 straight or branched chain alkyl group, ester group, amide group, carbonyl group, ether group, thioether group and thioester group ,

R ₁₀ and R ₁₁ are the same as or different from each other, and are each independently a valence bond, or a straight or branched chain alkyl group of C1 to C10,

Z is a valence bond, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C3 to C20 heterocycloalkyl group, substituted or unsubstituted C5 to C20 Is selected from an aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, and a substituted or unsubstituted C1 to C20 alkylamine group,

N = an integer of 3 to 6, x = an integer of 1 to 3.

The crosslinking agent represented by Formula 5 is preferably represented by any one selected from the following Formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 to 8,

이고,Y is

ego,

R ₁ is a hydrogen atom or an azide group,

A is a hydrogen atom or a halogen group,

R ₂ is a hydrogen atom or a C1 to C6 linear or branched alkyl group,

R ₃ is selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,

R ₄ is selected from a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- ,

R ₇ and R ₈ are the same as or different from each other, and are each independently selected from a valence bond, C1 to C10 straight or branched chain alkyl group, ester group, amide group, carbonyl group, ether group, thioether group and thioester group ,

Z is a valence bond, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C5 to C20 An aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group and a substituted or unsubstituted C1 to C20 alkylamine group,

The said x is an integer of 1-3.

According to another exemplary aspect of the present invention, the crosslinking agent; And a solution comprising a solvent.

According to another exemplary aspect of the present invention, the present invention relates to an organic film including the crosslinking agent.

According to another exemplary aspect of the present invention, it relates to an organic electronic device comprising the crosslinking agent.

According to various embodiments of the present invention, it is possible to provide a crosslinking agent having a high crosslinking efficiency while significantly reducing the amount of photocrosslinking initiator that may act as an impurity.

In addition, the crosslinking agent is excellent in the crosslinking efficiency in the solution process that is actively studied in the field of electronic devices, and can maintain sufficient solvent resistance, thereby showing an effect that can be applied to various device fields.

As used herein, "atom bond" means a single bond, a double bond or a triple bond unless otherwise defined.

The "substituted" means that at least one hydrogen atom is deuterium, C1 to C60 alkyl group, C3 to C60 cycloalkyl group, C2 to C60 heterocycloalkyl group, C1 to C60 halogenated alkyl group, C6 to C60 aryl group, C1 to C60 heteroaryl group, C1 to C60 alkoxy group, C2 to C60 alkenyl group, C2 to C60 alkynyl group, C6 to C60 aryloxy group, silyloxy group (-OSiH ₃ ), -OSiR ₁ H ₂ (R ₁ is C1 to C60 alkyl group or C6 to C60 aryl group), -OSiR ₁ R ₂ H (R ₁ and R ₂ are each independently a C1 to C60 alkyl group or C6 to C60 aryl group), -OSiR ₁ R ₂ R ₃ , (R ₁ , R ₂ , and R ₃ each independently represents a C1 to C60 alkyl group or a C6 to C60 aryl group), C1 to C60 acyl group, C2 to C60 acyloxy group, C2 to C60 heteroaryloxy group, C1 to C60 sulfonyl group, C1 to C60 alkylthiol group , C6 to C60 arylthiol group, C1 to C60 heterocyclothiol group, C1 to C60 phosphate amide group, silyl group (S iR ₁ R ₂ R ₃ ) (R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom, a C1 to C60 alkyl group or a C6 to C60 aryl group), an amine group (-NRR ') (here, R and R Are each independently a substituent selected from the group consisting of a hydrogen atom, a C1 to C60 alkyl group, and a C6 to C60 aryl group), a carboxyl group, a halogen group, a cyano group, a nitro group, an azo group, and a hydroxy group It means what is substituted by the substituent.

In addition, two adjacent substituents of the substituents may be fused to form a saturated or unsaturated ring.

In addition, the carbon number range of the alkyl group or the aryl group in the "substituted or unsubstituted C1 to C60 alkyl group" or "substituted or unsubstituted C6 to C60 aryl group", and the like, is unsubstituted without considering the substituted part of the substituent It means the total carbon number constituting the alkyl moiety or aryl moiety as viewed. For example, a phenyl group substituted with a butyl group in the para position means a aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

As used herein, "hetero" means one to four heteroatoms selected from the group consisting of N, O, S, and P in one functional group, and the remainder is carbon unless otherwise defined.

In the present specification, "hydrogen" means monotium, dihydrogen, or tritium unless otherwise defined.

As used herein, unless otherwise defined, an "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds. The alkyl group may be an "unsaturated alkyl group" containing at least one double or triple bond.

"Amine group" includes an amino group, an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group, and may be represented by -NRR ', wherein R and R' are each independently a hydrogen atom , A C1 to C60 alkyl group, and a C6 to C60 aryl group.

A "cycloalkyl group" includes monocyclic or fused polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.

"Heterocycloalkyl group" means containing 1 to 4 heteroatoms selected from the group consisting of N, O, S and P in the cycloalkyl group, and the rest are carbon. When the heterocycloalkyl group is a fused ring, at least one ring of the fused ring may include 1 to 4 heteroatoms.

An "aryl group" includes monocyclic or fused ring polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means containing 1 to 4 heteroatoms selected from the group consisting of N, O, S and P in the aryl group, the rest being carbon. When the heteroaryl group is a fused ring, at least one ring of the fused ring may include 1 to 4 heteroatoms.

The number of atoms of the ring in the aryl group and heteroaryl group is the sum of the carbon number and the number of non-carbon atoms.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

According to one aspect of the invention, there is provided a crosslinking agent represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

A, R ₁ and R ₂ are the same as or different from each other, and are each independently selected from a hydrogen atom, a halogen group, a C1 to C10 straight or branched chain alkyl group and an azide group,

이며,R ₅ and R ₆ are the same as or different from each other, and each independently a valence bond, a hydrogen atom, or

Is,

R ₃ and R ₃ ′ are the same as or different from each other, and are each independently selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,

R ₄ and R ₄ ′ are the same as or different from each other, and each independently a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- R ₉ -is selected from

R ₇ , R ₈ and R ₉ are the same as or different from each other, and each independently, a valence bond, a C1 to C10 straight or branched chain alkyl group, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thio s Selected from the

Z is a valence bond, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C5 to C20 aryl group, Substituted or unsubstituted C5 to C20 heteroaryl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C6 to C20 arylamine group, substituted or unsubstituted C1 to C20 heteroarylamine group, substituted Or an unsubstituted C1 to C20 alkylsilyl group, a substituted or unsubstituted C6 to C20 arylsilyl group, or a substituted or unsubstituted C5 to C20 heteroarylsilyl group,

N = an integer of 3 to 6, m = an integer of 1 to 2, x = an integer of 1 to 3.

Preferably, the crosslinking agent represented by Formula 1 may be represented by any one of the following Formulas 2 to 5.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,

이고,Y is

ego,

R ₁ is a hydrogen atom or an azide group,

A is a hydrogen atom or a halogen group,

R ₂ is a hydrogen atom or a C1 to C6 linear or branched alkyl group,

R ₃ is selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,

R ₄ is selected from a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- ,

R ₇ and R ₈ are the same as or different from each other, and are each independently selected from a valence bond, C1 to C10 straight or branched chain alkyl group, ester group, amide group, carbonyl group, ether group, thioether group and thioester group ,

R ₁₀ and R ₁₁ are the same as or different from each other, and are each independently a valence bond, or a straight or branched chain alkyl group of C1 to C10,

Z is a valence bond, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C5 to C20 Is selected from an aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, and a substituted or unsubstituted C1 to C20 alkylamine group,

N = an integer of 3 to 6, x = an integer of 1 to 3.

More preferably, the crosslinking agent represented by Formula 5 is represented by any one selected from the following Formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 to 8,

이고,Y is

ego,

R ₁ is a hydrogen atom or an azide group,

A is a hydrogen atom or a halogen group,

R ₂ is a hydrogen atom or a C1 to C6 linear or branched alkyl group,

R ₃ is selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,

R ₄ is selected from a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- ,

R ₇ and R ₈ are the same as or different from each other, and are each independently selected from a valence bond, C1 to C10 straight or branched chain alkyl group, ester group, amide group, carbonyl group, ether group, thioether group and thioester group ,

Z is a valence bond, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C5 to C20 An aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group and a substituted or unsubstituted C1 to C20 alkylamine group,

The said x is an integer of 1-3.

Still more preferably, the crosslinking agent represented by Formula 1 may be any one selected from Compounds 1 to 52 represented by the following Formula, but is not limited thereto.

An azide-type crosslinking agent according to an embodiment of the present invention may be a structure having three or more fluorinated phenyl azide (FPA) or phenyl acide (PA) in a molecular structure.

The azide crosslinking agent exhibits a higher crosslinking efficiency than the conventional crosslinking agent having one or two azide functional groups by increasing the number of azide groups acting as intramolecular crosslinking functional groups. Even small amounts of crosslinking agents can ensure high solvent resistance.

As the crosslinking agent of the present invention increases the crosslinking functional group in the molecule using triethylamine or acetonitrile, as shown in the following schemes (i) and (ii) showing one embodiment of the present invention, sodium azide, etc. By introducing an azide group into the crosslinking functional group by using, the final compound can be easily prepared, but the scope of the present invention is not limited thereto.

Reaction Scheme

[Scheme (ii)]

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the scope and contents of the present invention are not limited or interpreted by the following examples. In addition, if it is based on the disclosure of the present invention including the following examples, it will be apparent that those skilled in the art can easily carry out the present invention, the results of which are not specifically presented experimental results, these modifications and modifications are attached to the patent It goes without saying that it belongs to the claims.

In addition, the experimental results presented below are only representative of the experimental results of the Examples and Comparative Examples, and the effects of each of the various embodiments of the present invention not explicitly set forth below will be described in detail in the corresponding sections.

Example  1: Synthesis of Compound 3

Step 1 (see Scheme 1)

In a mixture of 1,2,3,4-tetrafluorobenzene (1 g, 6.7 mmol, 1 eq) and aluminum chloride (0.18 g, 1.3 mmol, 0.2 eq) under a nitrogen atmosphere, isopropyl chloride (1.1 g, 14 mmol, 2.1eq) was added and stirred at room temperature for 1 hour, then 3 ml of distilled water was added to stop the reaction and extracted with diethyl ether. The extract was washed with brine, dried over anhydrous magnesium sulfate, and used after removing the solvent without further purification.

¹ H NMR (500 MHz, Chloroform) δ 6.81 (dt, J = 8.1, 5.0 Hz, 1H), 3.18 (dt, J = 12.8, 6.4 Hz, 1H), 1.35 (d, J = 6.3 Hz, 6H).

Scheme 1

Step 2 (see Scheme 2)

The material of step 1 (1.0 g, 5.2 mmol, 1 eq) was added to 9 mL of anhydrous tetrahydrofuran cooled to −78 ° C. and stirred. N-BuLi (1.6M-hexane, 4.1ml, 6.2mmol, 1.2eq) was slowly added to the stirred solution, followed by stirring at -78 ° C for 4 hours. The resulting mixture was poured into 40 g of dry ice powder, stirred at room temperature for 1 hour, and then distilled water was added to terminate the reaction. After acidification the reaction was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Purification proceeded by washing with hexane.

¹ H NMR (500 MHz, Chloroform) δ 3.28 (dt, J = 12.5, 6.2 Hz, 1H), 1.37 (d, J = 6.4 Hz, 6H).

Scheme 2

Step 3 (see Scheme 3)

The material of step 2 (1 g, 4.2 mmol, 1 eq) was mixed with thionyl chloride (4 g, 33.9 mmol, 8 eq) and 1 drop of DMF under a nitrogen atmosphere and stirred while heating at 80 ° C. for 12 hours. Excess thionyl chloride was removed here under reduced pressure to give the product without further purification.

¹ H NMR (500 MHz, Chloroform) δ 3.00 (dt, J = 12.8, 6.5 Hz, 1H), 1.38 (d, J = 6.4 Hz, 6H).

Scheme 3

Step 4 (see Scheme 4)

Dissolve the step 3 material (0.72 g, 2.8 mmol, 3.8 eq) in anhydrous 1,4-dioxane (5 ml) under a nitrogen atmosphere. And triethylamine (0.3 g, 3 mmol, 4 eq) together with 2-ethyl-2- (hydroxy methyl) propane-1,3-diol (0.1 g, 0.7 mmol, 1 eq) under a nitrogen atmosphere. The solution dissolved in dioxane (5 ml) was added slowly with an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 4.47-4.43 (m, 8H), 3.07-3.03 (m, 3H), 1.67-1.54 (m, 3H), 1.44-1.31 (m, 25H), 1.03-0.99 ( m, 4H).

Scheme 4

Step 5 (see Scheme 5)

Sodium azide (0.1 g, 1.5 mmol, 4 eq) dissolved in acetone (1.2 ml) after dissolving the material (0.3 g, 0.4 mmol, 1 eq) prepared in step 4 in distilled water (1.2 ml) and acetone (1.7 ml) Was added. After reacting at a temperature of −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 4.45-4.41 (m, 8H), 3.05-3.01 (m, 3H), 1.66-1.53 (m, 3H), 1.42-1.29 (m, 25H), 1.02-0.98 ( m, 4H).

Scheme 5

Example 2: Synthesis of Compound 4

Step 1 (see Scheme 6)

N-succinimidyl-4-azido-2,3,5,6-tetrafluoro benzoate (2.15 g, 6.5 mmol, 3.8 eq) is dissolved in anhydrous acetonitrile (6 ml) under a nitrogen atmosphere. Then, 2- (amino methyl) -2-methyl propane-1,3-diamine (0.2 g, 1.7 mmol, 1 eq) dissolved in anhydrous acetonitrile (6 ml) was added under a nitrogen atmosphere, and reacted at room temperature for 6 hours. The white solid was obtained by filtration, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification proceeded to recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 7.70-7.66 (m, 1H), 3.66-3.62 (m, 1H), 3.21-3.17 (m, 1H), 1.32-1.28 (m, 1H).

Scheme 6

Example 3: Synthesis of Compound 12

Steps 1 to 3

It carried out by the same method as Example 1.

Step 4 (see Scheme 7)

In a nitrogen atmosphere, the material (0.94 g, 3.7 mmol, 5 eq) prepared in step 3 was dissolved in anhydrous 1,4-dioxane (7 ml). And triethylamine (0.39 g, 3,9 mmol, 5.3 eq) together with 2,2-bis (hydroxy methyl) propane-1,3-diol (0.1 g, 0.7 mmol, 1 eq) under a nitrogen atmosphere. The solution dissolved in 4-dioxane (7 ml) was added slowly with an ice bath. After 2 hours of reaction in an ice bath, it was further reacted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 6.98 (td, J = 7.9, 5.0 Hz, 1H), 4.44 (d, J = 13.6 Hz, 8H), 3.26-3.09 (m, 4H), 1.33 (dd, J = 10.1, 6.4 Hz, 24H).

Scheme 7

Step 5 (see Scheme 8)

Sodium azide (0.1 g, 1.5 mmol, 5 eq) dissolved in distilled water (1.2 ml) and acetone (1.7 ml) after dissolving the material (0.3 g, 0.3 mmol, 1 eq) prepared in step 4 in acetone (1.2 ml) Was added. After reacting at −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 6.95 (td, J = 7.9, 5.0 Hz, 1H), 4.42 (d, J = 13.6 Hz, 8H), 3.24-3.07 (m, 4H), 1.32 (dd, J = 10.1, 6.4 Hz, 24H).

Scheme 8

Example  4: Synthesis of Compound 15

Steps 1 to 3

It carried out by the same method as Example 1.

Step 4 (see Scheme 9)

Dissolve the material (0.79 g, 3.1 mmol, 4 eq) prepared in step 3 in anhydrous 1,4-dioxane (7 ml) under nitrogen atmosphere. And triethylamine (0.33 g, 3,3 mmol, 4.2 eq) together with 1,3,5-triazine-2,4,6-triol (0.1 g, 0.8 mmol, 1 eq) under a nitrogen atmosphere. The solution dissolved in 4-dioxane (7 ml) was added slowly with an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 3.14 (dt, J = 12.8, 6.4 Hz, 3H), 1.40 (d, J = 6.4 Hz, 18H).

Scheme 9

Step 5 (see Scheme 10)

Sodium azide (0.1 g, 1.5 mmol, 4 eq) dissolved in acetone (1.3 ml) after dissolving the material (0.3 g, 0.4 mmol, 1 eq) prepared in step 4 in distilled water (1.3 ml) and acetone (1.8 ml) Was added. And it reacted at -78 degreeC temperature for 24 hours. After removing the solvent, the mixture was extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

^{1 H} NMR (500 MHz, Chloroform) δ 3.14 (dt, J = 12.8, 6.4 Hz, 3H), 1.40 (d, J = 6.4 Hz, 18H).

Scheme 10

Example 5: Synthesis of Compound 16

Step 1 (see Scheme 11)

N-succinimidyl-4-azido-2,3,5,6-tetrafluoro benzoate (2 g, 6 mmol, 3.8 eq) is dissolved in anhydrous acetonitrile (6 ml) under a nitrogen atmosphere. 1,3,5-triazine-2,4,6-triamine (0.2 g, 1.6 mmol, 1 eq) dissolved in anhydrous acetonitrile (6 ml) was added under nitrogen and reacted at room temperature for 6 hours. After completion of the reaction, a white solid was obtained by filtration, extracted with distilled water and chloroform, dried over anhydrous magnesium sulfate, and purification proceeded to recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 7.86 (s, 3H).

Scheme 11

Example 6: Synthesis of Compound 22

Step 1 (see Scheme 12)

In a nitrogen atmosphere, 1,2,3,4,5-pentafluoro benzoyl chloride (0.307 g, 1.3 mmol, 4 eq) is dissolved in anhydrous 1,4-dioxane (3 ml). And 3,3 ', 3 "-((1,3,5-triazine-2,4,6-triyl) tris (azandiyl)) tris (propan-1-ol) (0.1 g, 0.3 mmol , 1eq) and triethylamine (0.14g, 1.4mmol, 4.2eq) dissolved in anhydrous 1,4-dioxane (3ml) under nitrogen atmosphere were slowly added to an ice bath for 2 hours. After the reaction was completed, the mixture was further reacted at room temperature for 22 hours, and after completion of the reaction, the white solids were removed by a filter, the solvent was removed, the mixture was extracted with distilled water, chloroform, and dried over anhydrous magnesium sulfate. Side reactions were removed.

¹ H NMR (500 MHz, Chloroform) δ 4.31 (t, J = 5.4 Hz, 6H), 3.35 (dt, J = 28.0, 5.6 Hz, 6H), 2.05-1.96 (m, 9H).

Scheme 12

Step 2 (see Scheme 13)

Sodium azide (0.06g, 0.9mmol, 4eq) dissolved in acetone (0.8ml) after dissolving the material (0.2g, 0.2mmol, 1eq) prepared in step 1 in distilled water (0.8ml) and acetone (1.1ml) Was added. After reacting at -78 ° C for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 4.30 (t, J = 5.4 Hz, 6H), 3.35 (dt, J = 28.0, 5.6 Hz, 6H), 2.04-1.95 (m, 9H).

Scheme 13

Example  7: Synthesis of Compound 26

N-succinimidyl-4-azido-2,3,5,6-tetrafluoro benzoate (1.2 g, 3.7 mmol, 3.8 eq) is dissolved in anhydrous acetonitrile (4 ml) under a nitrogen atmosphere. Then, butane-1,2,4-triamine (0.1 g, 1 mmol, 1 eq) dissolved in anhydrous acetonitrile (4 ml) was added under nitrogen atmosphere, and reacted at room temperature for 6 hours. After the reaction was completed, the white solid was obtained by filtration, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification proceeded to recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 6.24 (s, 1H), 5.94 (s, 1H), 5.64 (s, 1H), 4.31 (p, J = 6.8 Hz, 1H), 3.62 (dd, J = 12.5 , 6.8 Hz, 1H), 3.37 (dd, J = 12.5, 6.8 Hz, 1H), 3.24 (dt, J = 11.2, 7.5 Hz, 2H), 1.88 (ddd, J = 35.5, 14.4, 7.5 Hz, 2H) .

Scheme 14

Example 8: Synthesis of Compound 31

Steps 1 to 3

It carried out similarly to Example 1.

Step 4 (see Scheme 15)

Under nitrogen atmosphere, the material (0.66 g, 2.6 mmol, 4 eq) prepared in step 3 is dissolved in anhydrous 1,4-dioxane (5 ml). And triethylamine (0.28 g, 2,8 mmol, 4.2 eq) together with butane-1,2,4-tritriol (0.1 g, 0.6 mmol, 1 eq) in anhydrous 1,4-dioxane (5 ml) under nitrogen. The dissolved solution was slowly added to an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 3.50 (dd, J = 12.4, 5.2 Hz, 1H), 3.35 (dd, J = 12.4, 5.2 Hz, 1H), 3.15-2.98 (m, 3H), 2.96-2.85 (m, 3H), 2.59 (dd, J = 14.0, 7.4 Hz, 1H), 2.50 (dd, J = 13.9, 7.3 Hz, 1H), 1.43-1.35 (m, 18H).

Scheme 15

Step 5 (see Scheme 16)

Sodium azide (0.1 g, 1.5 mmol, 4 eq) dissolved in acetone (1.3 ml) after dissolving the material (0.3 g, 0.4 mmol, 1 eq) prepared in step 4 in distilled water (1.3 ml), acetone (1.8 ml) Was added. After reacting at −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 3.50 (dd, J = 12.4, 5.2 Hz, 1H), 3.35 (dd, J = 12.4, 5.2 Hz, 1H), 3.15-2.98 (m, 3H), 2.96-2.85 (m, 3H), 2.59 (dd, J = 14.0, 7.4 Hz, 1H), 2.50 (dd, J = 13.9, 7.3 Hz, 1H), 1.43-1.35 (m, 18H).

Scheme 16

Example 9: Synthesis of Compound 34

Steps 1 to 3

It carried out similarly to Example 1.

Step 4 (see Scheme 17)

In a nitrogen atmosphere, the material (1.04 g, 4.1 mmol, 5 eq) prepared in step 3 is dissolved in anhydrous 1,4-dioxane (8 ml). And triethylamine (0.44 g, 4,4 mmol, 5.3 eq) together with butane-1,2,3,4-tetraol (0.1 g, 0.8 mmol, 1 eq) in anhydrous 1,4-dioxane ( 8 ml) was slowly added into an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 5.80-5.70 (m, 1H), 4.84-4.63 (m, 1H), 4.58-4.37 (m, 1H), 3.20-3.05 (m, 2H), 1.36 (dd, J = 14.3, 6.3 Hz, 12H).

Scheme 17

Step 5 (see Scheme 18)

Sodium azide (0.1 g, 1.5 mmol, 5 eq) dissolved in acetone (1.1 ml) after dissolving the material (0.3 g, 0.3 mmol, 1 eq) prepared in step 4 in distilled water (1.1 ml) and acetone (1.6 ml) Was added. After reaction at -78 ° C for 24 hours to remove the solvent, the mixture was extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 5.80-5.70 (m, 1H), 4.84-4.63 (m, 1H), 4.58-4.37 (m, 1H), 3.20-3.05 (m, 2H), 1.36 (dd, J = 14.3, 6.3 Hz, 12H).

Scheme 18

Example 10: Synthesis of Compound 36

Step 1 (see Scheme 19)

1,2,3,4,5-pentafluoro benzoyl chloride (0.91 g, 3.9 mmol, 6 eq) is dissolved in anhydrous 1,4-dioxane (8 ml) under nitrogen atmosphere. And triethylamine (0.43 g, 4.3 mmol, 6.5 eq) together with pentane-1,2,3,4,5-phenol (0.1 g, 0.7 mmol, 1 eq) under anhydrous 1,4-dioxane (8 ml) ) Was slowly added to an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 5.27-5.15 (m, 3H), 4.77 (dd, J = 12.3, 5.6 Hz, 2H), 4.50 (dd, J = 12.4, 5.6 Hz, 2H).

Scheme 19

Step 2 (see Scheme 20)

Sodium azide (0.035g, 0.5mmol, 6eq) dissolved in acetone (0.5ml) after dissolving the material (0.1g, 0.1mmol, 1eq) prepared in step 1 in distilled water (0.5ml) and acetone (0.9ml) Was added. After reacting at −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 5.26-5.14 (m, 3H), 4.75 (dd, J = 12.3, 5.6 Hz, 2H), 4.50 (dd, J = 12.4, 5.6 Hz, 2H).

Scheme 20

Example 11: Synthesis of Compound 39

Step 1 (see Scheme 21)

In a nitrogen atmosphere, 1,2,3,4,5-pentafluorophenol (0.09 g, 0.5 mmol, 1 eq) is dissolved in anhydrous 1,4-dioxane (3 ml). In addition, octanediol dichloride (0.1 g, 0.5 mmol, 5 eq) and triethylamine (0.26 g, 2.6 mmol, 5.5 eq) were dissolved in anhydrous 1,4-dioxane (3 ml) under a nitrogen atmosphere. Was added slowly. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 2.72-2.68 (m, 1H), 2.54-2.50 (m, 1H), 1.75-1.64 (m, 2H), 1.40-1.35 (m, 2H).

Scheme 21

Step 2 (see Scheme 22)

In a nitrogen atmosphere, the material of step 1 (0.676 g, 1.9 mmol, 4 eq) is dissolved in anhydrous 1,4-dioxane (3 ml). And triethylamine (0.2 g, 2 mmol, 4.2 eq) together with butane-1,2,4-triol (0.05 g, 0.5 mmol, 1 eq) in anhydrous 1,4-dioxane (3 ml) under nitrogen atmosphere. The solution was slowly added to an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 5.24 (s, 1H), 4.34 (s, 1H), 4.03 (t, J = 5.3 Hz, 3H), 2.60-2.56 (m, 6H), 2.42-2.36 (m , 6H), 1.82 (d, J = 3.6 Hz, 2H), 1.78-1.73 (m, 2H), 1.73-1.66 (m, 10H), 1.39-1.34 (m, 4H), 1.33-1.28 (m, 6H ), 1.15-1.11 (m, 2H).

Scheme 22

Step 3 (see Scheme 23)

Sodium azide (0.048g, 0.7mmol, 4eq) dissolved in acetone (0.8ml) after dissolving the material (0.2g, 0.2mmol, 1eq) prepared in step 2 in distilled water (0.8ml) and acetone (1.1ml) Was added. After reacting at −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 5.21 (s, 1H), 4.31 (s, 1H), 4.00 (t, J = 5.3 Hz, 3H), 2.58-2.54 (m, 6H), 2.41-2.35 (m , 6H), 1.79 (d, J = 3.6 Hz, 2H), 1.76-1.71 (m, 2H), 1.71-1.64 (m, 10H), 1.38-1.33 (m, 4H), 1.31-1.26 (m, 6H ), 1.15-1.11 (m, 2H).

Scheme 23

Example  12: Synthesis of Compound 44

Steps 1 to 3

It carried out similarly to Example 1.

Step 4 (see Scheme 24)

Under nitrogen atmosphere, the material (0.77 g, 3 mmol, 4 eq) prepared in step 3 is dissolved in anhydrous 1,4-dioxane (6 ml). And triethylamine (0.32 g, 3,2 mmol, 4.2 eq) together with cyclohexane-1,3,5-triol (0.1 g, 0.8 mmol, 1 eq) under nitrogen anhydrous 1,4-dioxane (6 ml) The solution dissolved in was slowly added to an ice bath. After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (500 MHz, Chloroform) δ 4.47-4.43 (m, 3H), 3.06-3.02 (m, 3H), 2.44-2.40 (m, 3H), 1.87-1.83 (m, 3H), 1.46-1.32 ( m, 21 H).

Scheme 24

Step 5 (see Scheme 25)

Sodium azide (0.09 g, 1.4 mmol, 4 eq) dissolved in acetone (1.1 ml) after dissolving the material (0.3 g, 0.4 mmol, 1 eq) prepared in step 4 in distilled water (1.1 ml) and acetone (1.6 ml) Was added. After reacting at −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 4.46-4.42 (m, 3H), 3.05-3.01 (m, 3H), 2.43-2.39 (m, 3H), 1.87-1.83 (m, 3H), 1.45-1.31 ( m, 21 H).

Scheme 25

Example  13: Synthesis of Compound 45

Step 1 (see Scheme 26)

N-succinimidyl-4-azido-2,3,5,6-tetrafluoro benzoate (1 g, 2.9 mmol, 3.8 eq) is dissolved in anhydrous acetonitrile (4 ml) under a nitrogen atmosphere. In addition, cyclohexane-1,3,5-triamine (0.1 g, 0.8 mmol, 1 eq) dissolved in anhydrous acetonitrile (4 ml) was added under a nitrogen atmosphere, and reacted at room temperature for 6 hours. After the reaction was completed, a white solid was obtained by filtration, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification proceeded to recrystallization.

¹ H NMR (500 MHz, Chloroform) δ 5.43-5.39 (m, 3H), 3.57-3.53 (m, 3H), 2.52-2.48 (m, 3H), 2.34-2.30 (m, 3H).

Scheme 26

Comparative Example 1: Synthesis of FPA-1

Step 1 (see Scheme 27)

1,2,3,4,5-pentafluorobenzoyl chloride (0.9 g, 3.9 mmol, 2.2 eq) is dissolved in anhydrous diethyl ether (8 ml) under a nitrogen atmosphere. Then, a solution of triethylamine (0.4 g, 4 mmol, 2.2 eq) and ethylene glycol (0.1 g, 1.6 mmol, 1 eq) in anhydrous diethyl ether (8 ml) under nitrogen atmosphere was slowly added to an ice bath. . After 2 hours of reaction in an ice bath, the reaction was further conducted at room temperature for 22 hours. After the reaction was completed, the white solids were removed by a filter, the solvent was removed, extracted with distilled water and chloroform and dried over anhydrous magnesium sulfate. Purification was carried out by chromatography on silica gel to remove side reactions.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.71 (s, 4H).

Scheme 27

Step 2 (see Scheme 28)

Sodium azide (0.15 g, 2.3 mmol, 2.1 eq) dissolved in acetone (1.1 ml) after dissolving the material (0.5 g, 1.1 mmol, 1 eq) prepared in step 1 in distilled water (1.1 ml) and acetone (1.5 ml) ) Was added. After reacting at −78 ° C. for 24 hours, the solvent was removed, extracted with distilled water and chloroform, and dried over anhydrous magnesium sulfate. Purification was performed by chromatography on silica gel and recrystallization.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.69 (s, 4H).

Scheme 28

Test Example 1 Analysis of Crosslinking Efficiency (Solvent Resistance)

Crosslinking efficiency analysis was carried out in the solution of styrene polymer (Mn 11,000, PDI ≤1.1) dissolved in chlorobenzene at the concentration of 10mg / 1ml FPA-1 of Comparative Example 1, Examples 2, 3, 6, 9, 10 And crosslinking agents of compounds 4, 12, 22, 34, 36, and 39 of 11 at a weight ratio of 1% relative to the polymer, and then a film having a thickness of about 100 nm was formed by spin coating, and a film obtained by evaporating chlorobenzene was obtained. It is photocrosslinked by adding UV light of 254 nm and 300 mJ / cm ² under nitrogen atmosphere. Immediately after crosslinking, the film retention ratio was observed by immersing in UV intensity and chlorobenzene for 5 minutes and comparing the UV absorbance. Based on this, the crosslinking efficiency was analyzed. The solvent resistance results are shown in Table 1 below.

division Relative ratio of crosslinking functional groups by weight Crosslinking Efficiency (%) Comparative Example 1 1.00 78 Example 1 0.95 99 Example 2 0.90 95 Example 3 0.78 87 Example 4 0.91 90 Example 5 1.00 85 Example 6 0.65 87 Example 7 0.87 95

Referring to Table 1, the crosslinking efficiency according to the ratio of the number of crosslinking functional groups in consideration of the number of moles in comparison with the comparative compound under the same weight condition is analyzed. It turns out that it has high crosslinking efficiency. However, when comparing Compound 34 and Compound 36, Compound 36 has more crosslinking functionalities than Compound 34, but the crosslinking efficiency is lower than that of Compound 34. Accordingly, there is an appropriate number of crosslinking functional groups in the molecular structure to obtain a high crosslinking efficiency, and when the result table is viewed, the number of suitable crosslinking functional groups is 3-4. These results indicate that the multifunctional crosslinking compound of the present invention can secure the same solvent resistance while using a relatively small amount due to high crosslinking efficiency, thereby reducing the amount of crosslinking agent that can act as an impurity in the solution process. Indicates a more suitable material for the solution process.

Accordingly, according to various embodiments of the present invention, it is possible to provide a crosslinking agent having a high crosslinking efficiency while significantly reducing the amount of the photocrosslinking initiator that may act as an impurity.

In addition, the crosslinking agent not only has excellent crosslinking efficiency in a solution process that is being actively studied in the field of electronic devices, but also can maintain sufficient solvent resistance, thereby showing an effect applicable to various device fields.

Claims (7)

Crosslinking agent, characterized in that represented by any one of the formula
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,
Y is

ego,
R ₁ is a hydrogen atom or an azide group,
A is a hydrogen atom or a halogen group,
R ₂ is a hydrogen atom or a C1 to C6 linear or branched alkyl group,
R ₃ is selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,
R ₄ is selected from a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- ,
R ₇ and R ₈ are the same as or different from each other, and are each independently selected from a valence bond, a C1 to C10 linear or branched alkyl group, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group; ,
R ₁₀ and R ₁₁ are the same as or different from each other, and are each independently a valence bond, or a straight or branched chain alkyl group of C1 to C10,
Z is a valence bond, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C3 to C20 heterocycloalkyl group, substituted or unsubstituted C5 to C20 Is selected from an aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, and a substituted or unsubstituted C1 to C20 alkylamine group,
N = an integer of 3 to 6, x = an integer of 1 to 3. delete The method of claim 1,
Crosslinking agent represented by the formula (5) is a crosslinking agent, characterized in that represented by any one selected from formulas 6 to 8:
[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 to 8,
Y is

ego,
R ₁ is a hydrogen atom or an azide group,
A is a hydrogen atom or a halogen group,
R ₂ is a hydrogen atom or a C1 to C6 linear or branched alkyl group,
R ₃ is selected from an oxygen atom, a nitrogen atom, a sulfur atom, an ester group, an amide group, a carbonyl group, an ether group, a thioether group, and a thioester group,
R ₄ is selected from a valence bond, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylamine group, and -R ₇ -R _8- ,
R ₇ and R ₈ are the same as or different from each other, and are each independently selected from a valence bond, C1 to C10 straight or branched chain alkyl group, ester group, amide group, carbonyl group, ether group, thioether group and thioester group ,
Z is a valence bond, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C3 to C20 heterocycloalkyl group, substituted or unsubstituted C5 to C20 An aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group and a substituted or unsubstituted C1 to C20 alkylamine group,
The said x is an integer of 1-3.
The method of claim 1,
Crosslinking agent represented by the formula (1) is a crosslinking agent, characterized in that any one selected from compounds 1 to 52:

Crosslinking agent according to any one of claims 1, 3 and 4; And a solvent.
An organic film comprising the crosslinking agent according to any one of claims 1, 3 and 4.
An organic electronic device comprising the crosslinking agent according to any one of claims 1, 3 and 4.