KR20220039405A - Polymer for organic insulating layer and organic thin film transistor comprising the same - Google Patents

Abstract

The present invention relates to a polymer represented by structural formula 1. Accordingly, the novel polymer, which is a material for an organic insulating layer of the present invention, can be applied as a gate insulating layer of an organic thin film transistor to lower threshold voltage and hysteresis and to have excellent electrical and thin film properties.

Description

Polymer for an organic insulating layer and an organic thin film transistor comprising the same

The present invention relates to a polymer for an organic insulating layer and an organic thin film transistor including the same, and more particularly, to a polymer for an organic insulating layer and an organic thin film transistor including the same as an organic insulating layer.

Since the organic thin film transistor can be manufactured at a low cost and can provide flexibility, it is attracting a lot of attention as a key driving device for various electronic devices such as organic light emitting devices and solar cells. The organic thin film transistor is basically composed of a substrate, a gate insulator, a gate electrode, an active layer of an organic semiconductor, a source electrode, a drain electrode, and the like. there is. Among them, the gate insulating layer is most strongly related to the performance of the organic thin film transistor. For reference, silicon oxide and polymer materials are mainly used as materials used for the gate insulating layer.

In order to apply a large-area, low-cost, flexible electronic device, an organic insulating layer, not an inorganic material, must be used. In order to obtain a high-performance organic thin film transistor including such an organic insulating layer, it is required to exhibit a high dielectric constant or to have a low surface energy, and a property that is not easily deteriorated by humidity, oxygen, etc. is also required. However, it is not yet possible to replace the silicon oxide gate insulating film because all of these requirements are not satisfied.

Korean Patent Publication No. 10-2014-0071884

It is an object of the present invention to provide a polymer, which is a material for an organic insulating layer, included in a high-performance organic thin film transistor having low threshold voltage and hysteresis, and excellent electrical and thin film characteristics.

Another object of the present invention is to provide a high-performance organic thin film transistor including, as an organic insulating layer, a polymer, which is a material for an organic insulating layer, having low threshold voltage and hysteresis, and excellent electrical and thin film properties.

According to one aspect of the invention,

A polymer represented by the following Structural Formula 1 is provided.

[Structural Formula 1]

In Structural Formula 1,

n1 is the number of repeating units,

k1, L1, m1 are mole fractions, real numbers in the range 0 ≤ k1 ≤ 1, 0 ≤ L1 ≤ 1, 0 ≤ m1 ≤ 1, k1 + L1 + m1 = 1,

R ¹ to R ⁵ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ¹ to R ⁵ is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,

P ¹ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

또는

이고,Q ¹ is

or

ego,

n2 is the number of repeating units,

P ² is a valence bond, a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C1 to C60 heterocycloalkylene group, a substituted or unsubstituted C6 to C60 an arylene group, or a substituted or unsubstituted C1 to C360 heteroarylene group,

R ¹⁰ to R ¹³ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ⁶ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

R ⁷ to R ⁹ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Preferably, R ¹ to R ⁵ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C10 fluoroalkyl group, or a substituted or unsubstituted C1 to C10 alkyl group, and R ¹ to R At least one of ⁵ may be a fluorine atom or a substituted or unsubstituted C1 to C10 fluoroalkyl group.

Preferably, P ¹ may be a C1 to C30 alkylene group, or a C6 to C30 arylene group.

이고, Preferably, P ² is

ego,

q1 or q2 are each independently an integer selected from 1 to 5,

R ¹⁴ to R ¹⁷ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

, 또는

이고,Q ² is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

, or

ego,

n3 is the number of repeating units,

R ¹⁸ to R ²¹ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

이고, R ²² is a substituted or unsubstituted C1 to C30 alkyl group, or

ego,

n4 is the number of repeating units,

k2, L2, m2 are mole fractions, real numbers in the range 0 ≤ k2 ≤ 1, 0 < L2 ≤ 1, 0 ≤ m2 ≤ 1, k2 + L2 + m2 = 1,

R ²³ to R ²⁷ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ²³ to R ²⁷ is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,

P ³ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

R ²⁸ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

R ²⁹ to R ³¹ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or It may be an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

,

,

,

,

, 또는

이고,Preferably, R ⁶ is a C1 to C30 alkyl group,

,

,

,

,

, or

ego,

q3 to q10 are each independently an integer selected from 1 to 10,

R ³² to R ³⁷ are each independently a hydrogen atom, a deuterium atom, a fluoro group, a chloro group, a bromo group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted a C1 to C30 silyloxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

이고, Q ³ and Q ⁴ are each independently a substituted or unsubstituted C1 to C30 alkyl group, or

ego,

n5 is the number of repeating units,

k3, L3, m3 are mole fractions, real numbers in the range 0 ≤ k3 ≤ 1, 0 ≤ L3 ≤ 1, 0 ≤ m3 ≤ 1, k3 + L3 + m3 = 1,

P ⁴ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

R ³⁸ to R ⁴² are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ³⁸ to R ⁴² is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,

R ⁴³ to R ⁴⁵ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group , a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

More preferably, the polymer represented by Structural Formula 1 may be any one selected from the following polymers 1 to 16.

The polymer may be used as a material for an organic insulating film of an organic thin film transistor.

According to another aspect of the present invention,

An organic thin film transistor including the polymer is provided.

The polymer may be included in the polymer insulating layer.

The organic thin film transistor may be any one selected from a bottom gate-top contact type, a bottom gate-bottom contact type, a top gate-top contact type, and a top gate-bottom contact type.

The polymer insulating layer may be formed to a thickness of 10 to 1,000 nm.

The novel polymer, which is a material for an organic insulating layer of the present invention, is a polymer prepared by polymerizing a styrene-based monomer having a fluorine atom or/and a polyfunctional cinnamate-based monomer capable of photocrosslinking, which is applied as a gate insulating layer of an organic thin film transistor to Voltage and hysteresis may be reduced, and excellent electrical properties and thin film properties may be obtained.

1 is a cross-sectional view showing a structure of a bottom gate-top contact type among organic thin film transistors to which a polymer for an organic insulating layer of the present invention is applied.

Since the present invention can apply various transformations and can have various embodiments, specific embodiments are illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, terms including ordinal numbers such as first, second, etc. to be used below may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is said that a certain component is "formed" or "stacked" on another component, it may be formed or laminated by being directly attached to the front surface or one surface on the surface of the other component, but in the middle It should be understood that there may be other components in the .

The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

As used herein, "substituted" means that at least one hydrogen atom is deuterium, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C1 to C30 halogenated alkyl group, C6 to C30 aryl group, C1 to C30 heteroaryl group, C1 to C30 alkoxy group, C2 to C30 alkenyl group, C2 to 30 alkynyl group, C6 to C30 aryloxy group, silyloxy group (-OSiH ₃ ), -OSiR ¹ H ₂ (R ¹ is a C1 to C30 alkyl group or C6 to C30 aryl group), -OSiR ¹ R ² H (R ¹ and R ² are each independently a C1 to C30 alkyl group or C6 to C30 aryl group), -OSiR ¹ R ² R ³ , (R ¹ , R ² , and R ³ is each independently a C1 to C30 alkyl group or C6 to C30 aryl group), C1 to C30 acyl group, C2 to C30 acyloxy group, C2 to C30 heteroaryloxy group, C1 to C30 sulfonyl group, C1 to C30 alkyl Thiol group, C6 to C30 arylthiol group, C1 to C30 heterocyclothiol group, C1 to C30 phosphate amide group, silyl group (-SiR ¹ R ² R ³ ₎ (R ¹ , R ² , and R ³ are each independently A hydrogen atom, a C1 to C30 alkyl group or a C6 to C30 aryl group), an amine group (-NRR') (wherein, R and R' are each independently a hydrogen atom, a C1 to C30 alkyl group, and a C6 to C30 aryl group. It means a substituent selected from the group), a carboxyl group, a halogen group, a cyano group, a nitro group, an azo group, and a substituent selected from the group consisting of a hydroxyl group.

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

In addition, the carbon number range of the alkyl group or aryl group in the "substituted or unsubstituted C1 to C30 alkyl group" or "substituted or unsubstituted C6 to C30 aryl group" is unsubstituted without considering the portion in which the substituent is substituted. It refers to the total number of carbon atoms constituting the alkyl part or the aryl part when viewed as formed. For example, a phenyl group substituted with a butyl group at the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In addition, in the "substituted or unsubstituted C6 to C30 fused aryl group", etc., the carbon number range of the fused aryl group is fused when viewed as unsubstituted without considering the substituted portion of the substituent to be additionally newly formed It refers to the total number of carbon atoms constituting the aryl moiety.

In the present specification, unless otherwise defined, "hetero" means that one functional group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon.

In the present specification, "combination thereof" means that, unless otherwise defined, two or more substituents are bonded to a linking group, or two or more substituents are condensed and bonded.

As used herein, "hydrogen" means singlet, deuterium, or tritium, unless otherwise defined.

As used herein, the term “alkyl group” refers to an aliphatic hydrocarbon group unless otherwise defined.

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 bond or triple bond.

"Alkenylene group" means a functional group in which at least two carbon atoms are composed of at least one carbon-carbon double bond, and "alkynylene group" means that at least two carbon atoms are at least one carbon-carbon triple It means a functional group consisting of a bond. Alkyl groups, whether saturated or unsaturated, can be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C30 alkyl group. More specifically, it may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. It indicates that it is selected from the group consisting of.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, a cyclo It means a butyl group, a cyclopentyl group, a cyclohexyl group, and the like.

"Amine group" includes an amino group, an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group, and may be expressed as -NRR', wherein R and R' are each independently a hydrogen atom. , a substituent selected from the group consisting of a C1 to C30 alkyl group, and a C6 to C30 aryl group.

"Cycloalkyl group" includes monocyclic or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

"Heterocycloalkyl group" means that the cycloalkyl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heterocycloalkyl group is a fused ring, at least one ring of the fused ring may include 1 to 4 hetero atoms.

"Aromatic group" means a functional group in which all elements of a ring-shaped functional group have p-orbitals, and these p-orbitals form a conjugate. Specific examples include an aryl group and a heteroaryl group.

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

"Heteroaryl group" means that the aryl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, at least one ring among the fused rings may include 1 to 4 hetero atoms.

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

When used in combination such as "alkylaryl group" or "arylalkyl group", each of the terms alkyl and aryl has the meaning and content indicated above.

The term "arylalkyl group" refers to an aryl substituted alkyl radical such as benzyl and is included in the alkyl group.

The term "alkylaryl group" refers to an alkyl substituted aryl radical and is included in the aryl group.

Hereinafter, the structure of the polymer for the organic insulating layer of the organic thin film transistor of the present invention will be described.

The polymer of the present invention is represented by the following structural formula (1).

[Structural Formula 1]

In Structural Formula 1,

n1 is the number of repeating units,

k1, L1, m1 are mole fractions, real numbers in the range 0 < k1 ≤ 1, 0 < L1 ≤ 1, 0 < m1 ≤ 1, k1 + L1 + m1 = 1,

R ¹ to R ⁵ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ¹ to R ⁵ is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,

P ¹ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

또는

이고,Q ¹ is

or

ego,

n2 is the number of repeating units,

P ² is a valence bond, a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C1 to C60 heterocycloalkylene group, a substituted or unsubstituted C6 to C60 an arylene group, or a substituted or unsubstituted C1 to C360 heteroarylene group,

R ¹⁰ to R ¹³ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ⁶ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

R ⁷ to R ⁹ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Preferably, R ¹ to R ⁵ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C10 fluoroalkyl group, or a substituted or unsubstituted C1 to C10 alkyl group, and R ¹ to R At least one of ⁵ may be a fluorine atom or a substituted or unsubstituted C1 to C10 fluoroalkyl group.

Preferably, P ¹ may be a C1 to C30 alkylene group, or a C6 to C30 arylene group.

이고, Preferably, P ² is

ego,

q1 or q2 are each independently an integer selected from 1 to 5,

R ¹⁴ to R ¹⁷ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

, 또는

이고,Q ² is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

, or

ego,

n3 is the number of repeating units,

R ¹⁸ to R ²¹ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

이고, R ²² is a substituted or unsubstituted C1 to C30 alkyl group, or

ego,

n4 is the number of repeating units,

k2, L2, m2 are mole fractions, real numbers in the range 0 ≤ k2 ≤ 1, 0 < L2 ≤ 1, 0 ≤ m2 ≤ 1, k2 + L2 + m2 = 1,

R ²³ to R ²⁷ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ²³ to R ²⁷ is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,

P ³ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

R ²⁸ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

R ²⁹ to R ³¹ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or It may be an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

,

,

,

,

, 또는

이고,Preferably, R ⁶ is a C1 to C30 alkyl group,

,

,

,

,

, or

ego,

q3 to q10 are each independently an integer selected from 1 to 10,

R ³² to R ³⁷ are each independently a hydrogen atom, a deuterium atom, a fluoro group, a chloro group, a bromo group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted a C1 to C30 silyloxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

이고, Q ³ and Q ⁴ are each independently a substituted or unsubstituted C1 to C30 alkyl group, or

ego,

n5 is the number of repeating units,

k3, L3, m3 are mole fractions, real numbers in the range 0 < k1 ≤ 1, 0 < L1 ≤ 1, 0 < m1 ≤ 1, k3 + L3 + m3 = 1,

P ⁴ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

R ³⁸ to R ⁴² are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ³⁸ to R ⁴² is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,

R ⁴³ to R ⁴⁵ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group , a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Examples of the substituted or unsubstituted C1 to C30 heteroaryl group include a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted thiophenyl group , substituted or unsubstituted pyrrolyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted imidazo[1,2-a]pyridinyl group, substituted or unsubstituted Benzimidazolyl group, substituted or unsubstituted indazolyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzo A thiophenyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted tetrazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted oxatriazolyl group group, a substituted or unsubstituted thiatriazolyl group, a substituted or unsubstituted benzotriazolyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted purinyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted phthalazinyl group, a substituted or unsubstituted naphpyridinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or An unsubstituted quinazolinyl group, a substituted or unsubstituted acridinyl group, or a substituted or unsubstituted phenanthrolinyl group, preferably a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted A substituted triazinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted imidazo [1] ,2-a] pyridinyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indazolyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenazinyl group, substituted or It may be an unsubstituted carbazolyl group, or a substituted or unsubstituted dibenzothiophenyl group.

More preferably, the polymer represented by Structural Formula 1 may be any one selected from the following polymers 1 to 16.

The polymer may be used as a material for an organic insulating film of an organic thin film transistor.

Hereinafter, the organic thin film transistor of the present invention will be described.

The organic thin film transistor of the present invention includes the above polymer.

The polymer may be included in the gate insulating layer.

The organic thin film transistor may have any one type selected from a bottom gate-top contact type, a bottom gate-bottom contact type, a top gate-top contact type, and a top gate-bottom contact type, and preferably the structure of FIG. It may be a bottom gate-top contact type with

The bottom gate-top contact type organic thin film transistor includes a substrate, a gate electrode formed on the substrate, a polymer insulating layer formed on the gate electrode, an organic semiconductor layer formed on the polymer insulating layer, and source/drain electrodes formed on the organic semiconductor layer includes

The substrate may be a plastic substrate, a glass substrate, a quartz substrate, or a silicon substrate.

The polymer insulating layer may be formed by spin coating, dip coating, printing method, inkjet or roll coating.

The polymer insulating layer is preferably formed to a thickness of 10 to 1000 nm, more preferably, may be formed to a thickness of 10 to 200 nm.

The gate electrode and the source/drain electrode may include any one selected from gold (Au), silver (Ag), aluminum (Al), nickel (Ni), molybdenum (Mo), tungsten (W), and indium tin oxide (ITO). It can be a material.

Hereinafter, a compound for an organic insulating layer of an organic thin film transistor according to the present invention and a method for manufacturing the same will be described through examples.

[Example]

The polyfunctional cinnamate-based polymer polymers capable of photocrosslinking or a styrenic monomer having a group containing a fluorine atom represented by the above formulas according to an embodiment of the present invention may be prepared through a radical polymerization reaction as shown in the reaction formula of Comparative Example 1 below. It may be manufactured, but is not limited thereto.

<Comparative Example 1> Synthesis of Comparative Compound 1

Styrene (2.0 g, 19.20 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.308 g, 0.99 mmol), tetrahydrofuran (3.0 ml) in a reactor under a nitrogen atmosphere After dissolving, the mixture was stirred at 40° C. for 12 hours. After that, the temperature of the reactant was lowered, precipitated in methyl alcohol (250 ml), and filtered to obtain a product. (1.31 g, yield = 65.5%)

¹ H NMR (400 MHz, CDCl ₃ ), δ (ppm): 8.13-7.66 (br, 1H), 7.4-6.1 (br, 4H), 2.36-0.82 (br, 3H).

<Example 1> Synthesis of compound 1

In a reactor under a nitrogen atmosphere, 4-fluorostyrene (2.0 g, 16.37 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.303 g, 0.98 mmol), tetrahydrofuran ( 3.0 ml) and stirred at 40 °C for 12 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (0.9 g, yield = 45%)

¹ H NMR (400 MHz, CDCl ₃ ), δ (ppm): 6.93-6.58 (br,2H), 6.57-6.40 (br, 2H), 1.8-1.0 (br, 3H).

<Example 2> Synthesis of compound 2

In a reactor under nitrogen atmosphere, 2,6-difluorostyrene (2.0 g, 14.27 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.264 g, 0.85 mmol), tetra It was dissolved in hydrofuran (3.0 ml) and stirred at 40° C. for 12 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (0.87 g, yield = 43.2%)

¹ H NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.0-6.7 (br, 2H), 6.7-6.2 (br, 1H), 2.8-1.6 (br, 3H).

<Example 3> Synthesis of compound 3

In a reactor under a nitrogen atmosphere, 4- (trifluoromethyl) styrene (2.0 g, 11.61 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.214 g, 0.69 mmol), After dissolving in tetrahydrofuran (2.5 ㎖) was stirred at 40 ℃ for 12 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.13 g, yield = 56.5%)

¹ H NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.6-6.4 (br, 4H), 2.0-1.4 (br, 3H).

<Example 4> Synthesis of compound 4

[Step 1]

In a reactor, 4-acetoxystyrene (10.0 g, 61 mmol) was dissolved in tetrahydrofuran (100 mL) and stirred at 0°C. Then, sodium hydroxide (6.1 g, 154 mmol) was dissolved in water (30 mL) to make an aqueous solution, and it was slowly dropped into the reactor. When all the starting materials disappeared on TLC, the pH was adjusted with 2M HCl (pH=7). After the reaction is completed, the mixture is extracted three times with distilled water and ethyl acetate, dried over anhydrous MgSO ₄ , and the solvent is removed by distillation under reduced pressure to obtain 4-vinylphenol. (6.9 g, yield = 92%).

¹ H NMR (400 MHz, CDCl ₃ ), δ (ppm): 9.53(s, 1H), 7.28(d, 2H), 6.73 (d, 2H),6.63 (q, J = 17.63 Hz, 1H), 5.59 (d, 1H), 5.04 (d, 1H).

[Step 2]

In a reactor under a nitrogen atmosphere, 4-vinylphenol (7.0 g, 57 mmol) and triethylamine (10.5 g, 104 mmol) were dissolved in tetrahydrofuran (50 mL) and stirred at 0°C. Thereafter, cinnamoyl chloride (9.6 g, 57 mmol) was dissolved in tetrahydrofuran (25 mL) and slowly put into a reactor, followed by stirring at 24° C. for 24 hours. When the reaction is finished, threityl ammonium chloride is filtered, tetrahydrofuran remaining in the reactor is removed by distillation under reduced pressure, extracted three times with distilled water and dichloromethane, dried over anhydrous MgSO ₄ , the solvent is removed by distillation under reduced pressure, and the column The product was purified by chromatography. (10.2 g, yield = 70%)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.88 (d, 1H), 7.641-7.617 (m, 2H), 7.478-7.437 (m, 5H), 7.146 (d, 2H), 6.78-6.70 (dd, 1H), 6.67 (d, 1H), 5.77 (d, 2H), 5.28 (d, 2H).

[Step 3]

In a reactor under a nitrogen atmosphere, 4-vinylbenzyl cinnamate (2.0 g, 79.9 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.147 g, 0.47 mmol), tetrahydrofuran (2.0 mL) and stirred at 40° C. for 12 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.28 g, yield = 64 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 8.189-5.853 (br, 11H), 2.214-1.65 (br, 1H), 1.32-0.938 (br, 2H).

<Example 5> Synthesis of compound 5

[Step 1]

In a reactor under a nitrogen atmosphere, methacrylic acid (7.0 g, 81 mmol) and triethylamine (14.8 g, 146 mmol) were dissolved in tetrahydrofuran (70 mL) and stirred at 0°C. Thereafter, cinnamoyl chloride (13.5 g, 81 mmol) was dissolved in tetrahydrofuran (35 mL), put into a reactor, and stirred at 24° C. for 24 hours. After the reaction is finished, threityl ammonium chloride is hung up, tetrahydrofuran remaining in the reactor is removed by distillation under reduced pressure, extracted three times with distilled water and dichloromethane, dried over anhydrous MgSO ₄ , the solvent is removed by distillation under reduced pressure, and the column The product was purified by chromatography. (14.5 g, yield = 57.8%)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.60 (dd, 2H), 7.48-7.33 (m, 4H), 6.43 (d, 1H), 6.18 (d, 1H), 6.31 ( s, 1H), 2.01 (s, 3H).

[Step 2]

Cinamic methacrylic anhydride (2.0 g, 92.4 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.17 g, 0.55 mmol), tetrahydro in a reactor under a nitrogen atmosphere It was dissolved in furan (3.0 ml) and stirred at 40° C. for 12 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.08 g, yield = 54 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.60-7.33 (br, 6H), 6.31 (br, 1H), 2.1-1.7 (br, 2H), 1.2-0.6 (br, 3H) ).

<Example 6> Synthesis of compound 6

In a reactor under a nitrogen atmosphere, 2,3,4,5-tripentafluorostyrene (1.0 g, 5.15 mmol), 4-vinylbenzyl cinnamate (3.0 g, 12.0 mmol), 2,2-azobis-4-methyl It was dissolved in oxy-2,4-dimethylvaleronitrile (0.095 g, 0.309 mmol) and tetrahydrofuran (4.0 mL) and stirred at 40° C. for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 ml) and filtered to obtain a product. (1.5 g, yield = 65 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.931-5.901 (br, 11H), 2.954-0.973 (br, 6H).

<Example 7> Synthesis of compound 7

In a reactor under a nitrogen atmosphere, 2,3,4,5-tripentafluorostyrene (1.0 g, 5.15 mmol), 4-vinylbenzyl cinnamate (1.28 g, 5.15 mmol), 2,2-azobis-4-methyl It was dissolved in oxy-2,4-dimethylvaleronitrile (0.095 g, 0.309 mmol) and tetrahydrofuran (2.5 mL) and stirred at 40° C. for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.1 g, yield = 48 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.931-5.901 (br, 11H), 2.954-0.973 (br, 6H).

<Example 8> Synthesis of compound 8

In a reactor under nitrogen atmosphere, 2,3,4,5-tripentafluorostyrene (1.0 g, 5.15 mmol), 4-vinylbenzyl cinnamate (0.55 g, 2.20 mmol), 2,2-azobis-4-methyl It was dissolved in oxy-2,4-dimethylvaleronitrile (0.095 g, 0.309 mmol) and tetrahydrofuran (2.0 mL) and stirred at 40° C. for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.6 g, yield = 69 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.931-5.901 (br, 11H), 2.954-0.973 (br, 6H).

<Example 9> Synthesis of compound 9

2,3,4,5-tripentafluorostyrene (1.5 g, 7.72 mmol), 4-vinylbenzyl cinnamate (3.86 g, 15.4 mmol), methyl methacrylate (0.258 g, 2.57 mmol) in a reactor under nitrogen atmosphere ), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.143 g, 0.463 mmol), was dissolved in tetrahydrofuran (7.0 mL) and stirred at 40° C. for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 ml) and filtered to obtain a product. (2.8 g, yield = 66 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): ): 7.828-5.825 (br, 11H), 3.90-3.72 (br, 3H), 2.836-0.912 (br, 11H).

<Example 10> Synthesis of compound 10

In a reactor under nitrogen atmosphere, 2,3,4,5-tripentafluorostyrene (1.5 g, 7.72 mmol), 4-vinylbenzyl cinnamate (3.86 g, 15.4 mmol), ethylene glycol phenyl ether methacrylate (0.531 g) , 2.57 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.143 g, 0.463 mmol), was dissolved in tetrahydrofuran (7.0 mL) and stirred at 40° C. for 6 hours. made it After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (3.0 g, yield = 59 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.906-5.981 (br, 16H), 4.61-4.22 (br, 4H), 2.881-0.968 (br, 11H).

<Example 11> Synthesis of compound 11

2,3,4,5-tripentafluorostyrene (1.5 g, 7.72 mmol), 4-vinylbenzyl cinnamate (3.86 g, 15.4 mmol), ethylene glycol phenyl ether (methacryloxymethyl) in a reactor under nitrogen atmosphere Bis(trimethylsiloxy)methylsilane (0.826 g, 2.57 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.143 g, 0.463 mmol), tetrahydrofuran (7.0 mL) ) and stirred at 40 °C for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (2.8 g, yield = 47 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.853-5.864 (br, 11H), 3.50-3.32 (br, 2HZ), 2.836-0.912 (br, 11H), 0.32-0.08 (br , 21H).

<Example 12> Synthesis of compound 12

[Step 1]

Dissolve in maleic anhydride (3.46 g, 35 mmol), bis(3-aminopropyl)-tetramethyldisiloxane (3.9 g, 16 mmol), and benzene (150 ml) in a reactor under a nitrogen atmosphere, and then at room temperature for 1 hour stirred. After that, zinc bromide (7.94 g, 35 mmol) and bis(trimethylsilyl)amine (7.7 g, 80 mmol) were dissolved in benzene (19 mL) and slowly put into a reactor, followed by stirring at 80°C for 2 hours. The reaction mixture was extracted three times with 0.5 N HCl aqueous solution and ethyl acetate, and extracted twice with NaHCO ₃ aqueous solution. Then, after drying over anhydrous MgSO ₄ , the solvent was removed by distillation under reduced pressure to obtain a product. (5.0 g, yield = 76 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 6.69 (s, 4H), 3.48 (t, J = 7.37 Hz, 4H), 1.56 (m, 4H), 0.45 (m, 4H) , 0.02 (s, 12H).

[Step 2]

Compound 6 (0.1 g), the product of step 1 (0.057 g), irgacure 819 [Photoinitiator] (0.0047 g) and F-554 [surfactant] (0.00786 g) were dissolved in toluene (9 ml) to make a solution. It was printed with a thickness of 40 nm using an EHD (Electrohydrodynamic) printing method. The printed film was subjected to photocrosslinking (254nm) bonding reaction, and then heat treated at 150°C for 30 minutes to obtain a final crosslinked insulator thin film.

<Example 13> Synthesis of compound 13

[Step 1]

In a reactor under a nitrogen atmosphere, 2-hydroxyethyl methacrylate (10.0 g, 76 mmol) and potassium tert-butoxide (17.24 g, 153 mmol) were dissolved in DMF (100 mL) and stirred at room temperature. After 1 hour, 1-bromo-4-chlorobenzene (14.71 g, 76 mmol) was dissolved in DMF (35 mL), put slowly in the reactor, and stirred at 90° C. for 12 hours. After the reaction was completed, the DMF remaining in the reactor was removed by distillation under reduced pressure, extracted three times with distilled water and dichloromethane, dried over anhydrous MgSO ₄ , the solvent was removed by distillation under reduced pressure, and the product was purified by column chromatography to obtain a product. (12.3 g, yield = 66.5%)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.38 (d, 2H), 7.03 (d, 2H), 6.48 (d, 1H), 6.40 (d, 1H), 4.52 (t, 2H), 4.42 (t, 2H), 2.01 (s, 3H).

[Step 2]

In a reactor under nitrogen atmosphere, 2,3,4,5-tripentafluorostyrene (1.5 g, 7.72 mmol), 4-vinylbenzyl cinnamate (3.86 g, 15.4 mmol), ethylene glycol phenyl ether methacrylate (0.531 g) , 2.57 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.143 g, 0.463 mmol), was dissolved in tetrahydrofuran (7.0 mL) and stirred at 40° C. for 6 hours. made it After that, the temperature of the reactant was lowered, precipitated in methyl alcohol (250 ml), and filtered to obtain a product. (3.0 g, yield = 59 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.906-5.981 (br, 16H), 4.61-4.22 (br, 4H), 2.881-0.968 (br, 11H).

<Example 14> Synthesis of compound 14

[Step 1]

2,3,4,5-tripentafluorostyrene (1.5 g, 7.72 mmol), 4-vinylbenzyl cinnamate (3.86 g, 15.4 mmol), glycidyl methacrylate (0.366 g, 2.57 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.143 g, 0.463 mmol), and tetrahydrofuran (7.0 mL) were dissolved and stirred at 40° C. for 6 hours. . After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (2.1 g, yield = 46 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.810-5.732 (br, 11H), 4.6-4.14 (br, 2H), 3.18-3.07 (br, 1H), 2.818-0.902 (br) , 13H).

[Step 2]

Compound 15 (1.0 g, 1.70 mmol) and butane-1,4-diamine (0.12 g, 13.6 mmol) were dissolved in NMP (1.0 mL) in a reactor under a nitrogen atmosphere, followed by stirring at 130° C. for 12 hours. After that, the temperature of the reactant was lowered and the NMP remaining in the reactor was removed by vacuum distillation to obtain a product. (0.7 g, yield = 60 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.67-5.652 (br, 22H), 4.95-4.22 (br, 6H), 3.65 (br, 2H), 2.73-0.894 (br, 32H) ).

<Example 15> Synthesis of compound 15

2,3,4,5-tripentafluorostyrene (2.0 g, 10.3 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.19 g, 0.61 mmol), dissolved in tetrahydrofuran (2.0 ml), and stirred at 40° C. for 12 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.4 g, yield = 70 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 2.85-1.80 (br, 3H).

<Example 16> Synthesis of compound 16

[Step 1]

After dissolving 7-hydroxy-4-methylcoumarin (5.44 g, 30.9 mmol) in THF (150 mL) in a reactor under a nitrogen atmosphere, 2-hydroxyethyl methacrylate (4.42 g, 34.0 mmol) and triphenylphos After adding pyrite (8.42 g, 32.1 mmol), the mixture was stirred at room temperature. Thereafter, diisopropyl azodicarbylate (6.37 g, 31.5 mmol) was slowly added thereto, followed by stirring at room temperature for 24 hours. Upon completion of the reaction, the solvent was removed by distillation under reduced pressure and purified by column chromatography to obtain a product. (6.77 g, yield = 76%)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.58 (d, 1H), 6.83 (d, 1H), 6.76 (s, 1H), 6.06 (d, 1H), 6.04 (s, 1H), 5.49 (d, 1H), 4.52 (t, 2H), 4.21 (t, 2H), 2.45 (s, 3H), 1.95 (s, 3H).

[Step 2]

2,3,4,5-tripentafluorostyrene (1.5 g, 7.72 mmol), 2-((4-methyl-2-oxo-2H-curmen-7-yl)oxy)ethyl in a reactor under nitrogen atmosphere After dissolving in methacrylate (5.19 g, 18.0 mmol), 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile (0.14 g, 0.46 mmol), tetrahydrofuran (4.0 ml) 40 It was stirred at ℃ for 6 hours. After lowering the temperature of the reactant, it was precipitated in methyl alcohol (250 mL) and filtered to obtain a product. (1.2 g, yield = 32 %)

¹ H NMR (400 MHz, CD ₂ Cl ₂ ), δ (ppm): 7.63-6.68 (br, 4H), 4.50-4.18 (br, 4H), 2.932-0.961 (br, 9H).

Device Example 1: Organic Thin Film Transistor Device Manufacturing

For the organic thin film transistor device, a glass wafer (Eagle-XG, iNexus. Inc) and polyethylene terephthalate (PET, XG532, PFC Ltd) were cut into a size of 2.0 x 2.0 cm ² and used as a device substrate. To wash impurities and organic matter on the substrate, ultrasonic cleaning was performed for 30 minutes in a beaker containing a mixture of acetone and isopropyl alcohol (Daesung Chemicals & Metals), and this operation was repeated twice. The washed substrate was dried well using a nitrogen gun (N ₂ gun) and then exposed to UV-ozone for 30 minutes. Thereafter, vacuum deposition was performed at a deposition rate of 2 Å/s, a vacuum pressure of 10 ⁻⁶ Torr, and a substrate temperature: 25° C. to form an Al-gate electrode pattern having a thickness of 30 nm. Compound 1 (gate insulating layer) was printed thereon to a thickness of 110 nm by using the EHD printing method. The printed film was subjected to light crosslinking (254 nm or 365 nm) and then heat treated at 150° C. for 30 minutes. C10-DNTT was used as the organic active layer of the device, and a 100 nm thick gold (Au) electrode was vacuum-deposited on the C10-DNTT for the source/drain electrode using a shadow mask. (Deposition rate: 0.1 - 0.2 Å/s, vacuum pressure: 10 ^-6 Torr, substrate temperature: 25 °C) The channel length ( L ) and width ( W ) were 100 and 300 µm, respectively. At this time, all device manufacturing environments were carried out in a glove box filled with nitrogen gas.

Device Example 2: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 2 was used instead of Compound 1 as the gate insulating layer compound.

Device Example 3: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 3 was used instead of Compound 1 as the gate insulating layer compound.

Device Example 4: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 4 was used instead of Compound 1 as the gate insulating layer compound.

Device Example 5: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 5 was used instead of Compound 1 as the gate insulating layer compound.

Device Example 6: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 6 was used as the gate insulating layer compound to a thickness of 40 nm.

Device Example 7: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 7 was used as the gate insulating layer compound to a thickness of 40 nm.

Device Example 8: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 8 was used instead of Compound 1 as the gate insulating layer compound.

Device Example 9: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 9 was used instead of Compound 1 as the gate insulating layer compound to a thickness of 40 nm.

Device Example 10: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 10 was used instead of Compound 1 as the gate insulating layer compound to have a thickness of 40 nm.

Device Example 11: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 11 was used instead of Compound 1 as the gate insulating layer compound to have a thickness of 40 nm.

Device Example 12: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 12 was used instead of Compound 1 as the gate insulating layer compound to have a thickness of 40 nm.

Device Example 13: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 13 was used instead of Compound 1 as the gate insulating layer compound to have a thickness of 40 nm.

Device Example 14: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 14 was used as the gate insulating layer compound to a thickness of 40 nm.

Device Example 15: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 15 was used instead of Compound 1 as the gate insulating layer compound.

Device Example 16: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Compound 16 was used instead of Compound 1 as the gate insulating layer compound.

Device Comparative Example 1: Organic Thin Film Transistor Device Manufacturing

An organic thin film transistor device was manufactured in the same manner as in Device Example 1, except that Comparative Compound 1 was used instead of Compound 1 as the gate insulating layer compound.

[Experimental example]

Experimental Example 1: Device Characteristic Analysis

(1) Confirmation of dielectric properties

The dielectric properties of the compounds of Examples 1 to 16 and Comparative Example 1 were measured using an HP LCR meter for the dielectric constant (C i ) and leakage current density per unit area at 1 KHz and DC 100V voltage for an area of 5.75 mm ² of the same thin film capacitor. measured.

(2) Check insulation properties

Examples 1 to 16, and the insulating properties of the compounds of Comparative Example 1, in order to measure the voltage at which dielectric breakdown occurs, the samples of Examples and Comparative Examples prepared above are spin-coated on an ITO substrate and then a DC voltage is applied to cause breakdown. The starting voltage was measured.

The measurement results are summarized in Table 1 below.

According to this, it was confirmed that the characteristics of the organic thin film transistors of Device Examples 1 to 16 of the present invention were superior to those of the organic thin film transistors of Device Comparative Example 1. In other words, it was found that the organic thin film transistor of the present invention had high capacitance density, high dielectric breakdown voltage, and low leakage current density. Accordingly, it was confirmed that the organic insulating film made of the polymer of the present invention can be effectively applied to various types of organic thin film transistors.

Claims (11)

A polymer represented by the following Structural Formula 1.
[Structural Formula 1]

In Structural Formula 1,
n1 is the number of repeating units,
k1, L1, m1 are mole fractions, real numbers in the range 0 < k1 ≤ 1, 0 < L1 ≤ 1, 0 < m1 ≤ 1, k1 + L1 + m1 = 1,
R ¹ to R ⁵ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ¹ to R ⁵ is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,
P ¹ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,
Q ¹ is

or

ego,
n2 is the number of repeating units,
P ² is a valence bond, a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C1 to C60 heterocycloalkylene group, a substituted or unsubstituted C6 to C60 an arylene group, or a substituted or unsubstituted C1 to C360 heteroarylene group,
R ¹⁰ to R ¹³ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
R ⁶ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,
R ⁷ to R ⁹ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. The method of claim 1,
R ¹ to R ⁵ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C10 fluoroalkyl group, or a substituted or unsubstituted C1 to C10 alkyl group, and at least any of R ¹ to R ⁵ One is a fluorine atom, or a substituted or unsubstituted C1 to C10 fluoroalkyl group. The method of claim 1,
P ¹ is a C1 to C30 alkylene group, or a C6 to C30 arylene group. The method of claim 1,
P ² is

ego,
q1 or q2 are each independently an integer selected from 1 to 5,
R ¹⁴ to R ¹⁷ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,
Q ² is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,

, or

ego,
n3 is the number of repeating units,
R ¹⁸ to R ²¹ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group,
R ²² is a substituted or unsubstituted C1 to C30 alkyl group, or

ego,
n4 is the number of repeating units,
k2, L2, m2 are mole fractions, real numbers in the range 0 ≤ k2 ≤ 1, 0 < L2 ≤ 1, 0 ≤ m2 ≤ 1, k2 + L2 + m2 = 1,
R ²³ to R ²⁷ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ²³ to R ²⁷ is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,
P ³ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,
R ²⁸ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,
R ²⁹ to R ³¹ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or An unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. The method of claim 1,
R ⁶ is a C1 to C30 alkyl group,

,

,

,

,

, or

ego,
q3 to q10 are each independently an integer selected from 1 to 10,
R ³² to R ³⁷ are each independently a hydrogen atom, a deuterium atom, a fluoro group, a chloro group, a bromo group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted a C1 to C30 silyloxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
Q ³ and Q ⁴ are each independently a substituted or unsubstituted C1 to C30 alkyl group, or

ego,
n5 is the number of repeating units,
k3, L3, m3 are mole fractions, real numbers in the range 0 ≤ k3 ≤ 1, 0 ≤ L3 ≤ 1, 0 ≤ m3 ≤ 1, k3 + L3 + m3 = 1,
P ⁴ is a valence bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C1 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 an arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,
R ³⁸ to R ⁴² are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group , a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and at least one of R ³⁸ to R ⁴² is a fluorine atom , or a substituted or unsubstituted C1 to C30 fluoroalkyl group,
R ⁴³ to R ⁴⁵ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group , a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. The method of claim 1,
The polymer represented by the structural formula 1 is a polymer, characterized in that any one selected from the following polymers 1 to 16.

The method of claim 1,
The polymer is a polymer, characterized in that used as a material of the organic insulating film of the organic thin film transistor. An organic thin film transistor comprising the polymer of any one of claims 1 to 7. 9. The method of claim 8,
The polymer is an organic thin film transistor, characterized in that contained in the polymer insulating layer. 9. The method of claim 8,
The organic thin film transistor is any one selected from a bottom gate-top contact type, a bottom gate-bottom contact type, a top gate-top contact type, and a top gate-bottom contact type. 9. The method of claim 8,
The polymer insulating layer is an organic thin film transistor, characterized in that formed to a thickness of 10 to 1,000 nm.

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