JP2021031621A - Acrylic polymer, light-emitting material and organic light-emitting element - Google Patents

Abstract

To provide a light-emitting material that has a high light-emitting efficiency, and, in addition, that can, by using a coating method, form a stable amorphous film.SOLUTION: An acrylic polymer of the present invention emits delayed fluorescence. This acrylic polymer is composed of, for example, a structural unit in which a structure capable of emitting delayed fluorescence is introduced into a side chain, and a structural unit in which a structure capable of emitting delayed fluorescence is not introduced into the side chain. As a structure capable of emitting delayed fluorescence, a moiety containing a donor group and an acceptor group can be used.SELECTED DRAWING: Figure 1

Description

The present invention relates to an acrylic polymer useful as a light emitting material and an organic light emitting device using the acrylic polymer.

The organic electroluminescence element (organic EL element) is an organic light emitting element that emits light by radiation deactivation of excitons generated by current excitation of the organic light emitting layer. Here, in current excitation, singlet excitons and triplet excitons are generated with a probability of 25%: 75% according to the spin statistical law, but the radiation deactivation from the excited triplet state to the base singlet state is originally It is a forbidden transition. Therefore, in ordinary organic light-emitting materials, triplet excitons are heat-deactivated before radiation deactivation, and only singlet excitons generated with a 25% probability can be used for light emission, which limits the improvement of luminous efficiency. was there.
Therefore, as a result of research on light emitting materials in order to break the limit of such emission efficiency, phosphorescent materials that can use triplet excitons for light emission and triplet exciters are converted into singlet excitors. A thermally activated delayed fluorescent material (TADF) that can be used for light emission has been developed, and it is possible to convert singlet and triplet excitons generated by current excitation into light with 100% efficiency. It has become. Among them, the thermally activated delayed fluorescent material is highly versatile and reduces the cost of the organic EL element because high luminous efficiency can be obtained without using expensive elements such as iridium and platinum which are usually contained in phosphorescent materials. Further development is being energetically promoted because it contributes to.

By the way, the vacuum vapor deposition method is often used for forming an organic film such as a light emitting layer constituting an organic EL element. However, the vacuum vapor deposition method has a problem that the running cost of the apparatus is relatively high because a large amount of electric power is required to maintain the vacuum and generate heat for vapor deposition. Therefore, as a low-cost film forming method instead of the vacuum vapor deposition method, the adoption of a coating method in which a liquid material is thinly coated to form a film is being studied (see, for example, Patent Document 1).

JP-A-2019-119723

As described above, it is considered to adopt a coating method as a method for forming an organic film of an organic EL element. However, as a result of studies by the present inventors, it has been found that the following inconveniences occur when the light emitting material used in the vacuum vapor deposition method is directly diverted to the coating method to form a light emitting layer.
That is, the organic film of the organic EL element is usually formed as an amorphous film because it is easy to obtain good surface smoothness and homogeneous properties. Here, in order to form an amorphous film by the coating method, the material has sufficiently high solubility in a solvent in order to prevent crystallization of the film during the film formation process and after the film formation, and the film formation It is particularly important that the subsequent amorphous film is stable without causing phase separation or aggregation. However, the conventional light-emitting material, which is premised on film formation by the vacuum vapor deposition method, is not molecularly designed in consideration of solubility, and therefore has insufficient solubility for use in the coating method. Therefore, there is a problem that it is difficult to form an amorphous light emitting layer by the coating method and to stably maintain the amorphous structure of the light emitting layer formed by the coating method. Further, the light emitting material is generally provided to the light emitting layer in combination with another material such as a host. However, when another material is mixed with the conventional light emitting material and formed by a coating method, crystals after the formation are particularly formed. There is also the problem that crystallization and phase separation are likely to occur.

Under such circumstances, the present inventors have high luminous efficiency, can easily form a film as an amorphous film by a coating method, and further maintain the formed amorphous structure stably. We have conducted research with the aim of providing a light-emitting material. Then, we proceeded with diligent studies for the purpose of providing an inexpensive organic light emitting device showing high luminous efficiency.

As a result of diligent studies, the present inventors have found that an acrylic polymer in which a delayed fluorescent substance residue is introduced into a constituent unit has high luminous efficiency and high solubility in a solvent, and uses a coating method. It has been found that a stable amorphous film can be formed. The present invention has been proposed based on such findings, and specifically has the following configuration.

[1] An acrylic polymer that emits delayed fluorescence.
[2] The acrylic polymer according to [1], which has a partial structure containing an electron donor group and an electron acceptor group in a side chain.
[3] The acrylic polymer according to [1] or [2], which comprises a structural unit represented by the following general formula (1).
[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, DF represents a group capable of emitting delayed fluorescence, and L represents a single bond or a divalent linking group. ]
[4] The acrylic polymer according to [3], wherein the DF of the general formula (1) is a group represented by the following general formula (1a) or the following general formula (1b).
General formula (1a)
A ¹ − D ¹ ― * ¹
General formula (1b)
D ^2- A ^2- * ²
[In the general formulas (1a) and (1b), D ¹ and D ² each independently represent a donor group, and A ¹ and A ² each independently represent an acceptor group. * ¹ and * ² represent the bonding position to L in the general formula (1). ]
[5] The acrylic polymer according to [3], wherein the DF of the general formula (1) is a group represented by any of the following formulas.
[In each equation, * represents the position of connection to L in the general equation (1). The hydrogen atom in the formula may be substituted with a substituent. ]
[6] Described in any one of [3] to [5], which is a copolymer containing the structural unit represented by the general formula (1) and the structural unit represented by the following general formula (3). Acrylic polymer.
[In the general formula (3), R ² represents a hydrogen atom or a methyl group, and R ³ represents a substituted or unsubstituted alkyl group. ]
[7] A luminescent material containing the acrylic polymer according to any one of [1] to [6].
[8] A film containing the acrylic polymer according to any one of [1] to [6].
[9] The film according to [8], which is a coating film of the acrylic polymer.
[10] The film according to [8] or [9], which is an amorphous film.
[11] The film according to any one of [8] to [10], wherein the glass transition temperature Tg is 115 ° C. or higher.
[12] An organic light emitting device containing the acrylic polymer according to any one of [1] to [6].
[13] The organic light emitting device according to [12], wherein the acrylic polymer is contained in a light emitting layer.
[14] The organic light emitting device according to [12] or [13], which is an organic electroluminescence device.

The acrylic polymer of the present invention has high luminous efficiency and can be formed into a stable amorphous film by a coating method. Therefore, the acrylic polymer of the present invention is useful as a light emitting material. Further, by using the acrylic polymer of the present invention as the material of the organic layer, it is possible to realize an inexpensive organic light emitting device having high luminous efficiency.

It is the schematic sectional drawing which shows the layer structure example of the organic electroluminescence element.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
The isotope species of hydrogen atoms present in the molecule of the acrylic polymer of the present invention are not particularly limited, and for example, all hydrogen atoms in the molecule ^{may be 1} H, or some or all of them may be ² H (duterium). D) may be used. Further, in the present specification, when the term "(meth) acryloyloxy group" is used, both the acryloyloxy group and the methacryloyloxy group are included, and when the term "(meth) acrylate" is used, the term acrylate is used. And methacrylate should be included.
In the present specification, the "fluorescent material" is a luminescent material in which the emission intensity of fluorescence is higher than the emission intensity of phosphorescence when luminescence is observed at 20 ° C., and the "phosphorescent material" is a luminescent material. When luminescence is observed at 20 ° C., the luminescence material has a higher luminescence intensity of phosphorescence than the luminescence intensity of fluorescence. The "delayed fluorescent material" is a material that emits light from an excited singlet, and is a material in which both fluorescence having a short emission lifetime at 20 ° C. and fluorescence having a long emission lifetime (delayed fluorescence) are observed. Normal fluorescence (fluorescence that is not delayed fluorescence) is a material that emits light from an excited singlet and has an emission lifetime of ns order, and phosphorescence is a material that emits light from a triplet and usually has an emission lifetime. It is more than μs order. Further, in the present specification, "intersystem crossing" means a conversion from an excited triplet state to an excited singlet state.

<Acrylic polymer>
The acrylic polymer of the present invention is an acrylic polymer that emits delayed fluorescence. Here, the "acrylic polymer" refers to a polymer of a monomer (acrylic monomer) having a (meth) acryloyloxy group. That is, the acrylic polymer of the present invention is a polymer of a monomer having a (meth) acryloyloxy group and can emit delayed fluorescence.
"Delayed fluorescence" is the fluorescence emitted when the inverse intersystem crossing from the excited triplet state to the excited singlet state occurs and then returns from the excited singlet state to the ground state, and is the directly generated excited singlet. It is the fluorescence observed later than the fluorescence from the singlet state (normal fluorescence). In the present invention, when the transient decay curve of light emission due to photoexcitation is measured at 20 ° C. for the target acrylic polymer, a light emitting component (delayed fluorescence) having a light emission lifetime of 100 ns or more is observed. It is determined that the acrylic polymer emits radiation. Further, in the present invention, an acrylic polymer having a structure capable of emitting delayed fluorescence introduced into a constituent unit is also included in the "acrylic polymer that emits delayed fluorescence". Here, the "structure capable of emitting delayed fluorescence" is a structure that imparts delayed fluorescence radioactivity to the acrylic polymer, and is an atomic group (partial structure) composed of the main structure of the delayed fluorescent substance, or a donor group and an acceptor group. Atomic groups (partial structures) containing the above can be mentioned. The acrylic polymer of the present invention may contain such a partial structure having delayed fluorescent radioactivity in at least one structural unit, and it is preferable that the partial structure having delayed fluorescent radioactivity is contained in the side chain of the polymer chain. .. In the following description, a structure capable of emitting delayed fluorescence is referred to as a “TADF structure”, a structural unit including a structure capable of emitting delayed fluorescence is referred to as a “TADF-containing structural unit”, and a “TADF-containing structural unit” is obtained by polymerization. The substrate that becomes "TADF-containing monomer" is called. Further, a structural unit that does not contain a structure capable of emitting delayed fluorescence is referred to as a “TADF-free structural unit”, and a substrate that becomes a “TADF-free structural unit” by polymerization is referred to as a “TADF-free monomer”.

In the "partial structure consisting of the main structure of the delayed fluorescent substance" as the TADF structure, the "delayed fluorescent substance" refers to a compound that can emit delayed fluorescence by itself, and is referred to as the "main structure of the delayed fluorescent substance". Refers to the remaining portion (residue) of the delayed fluorescent substance excluding the hydrogen atom at the position where it forms a covalent bond with other atomic groups.

Further, in the "partial structure including a donor group and an acceptor group" as a TADF structure, the "donor group" is a group that donates an electron to an atomic group to which the donor group is bonded. Means. For example, it can be selected from substituents with a negative _{Hammett σ p value.} An "acceptor group" is a group that attracts electrons to a group of atoms to which an acceptor group is bonded. For example, you can choose from substituents that have a positive _{Hammett σ p value.}
Here, the "sigma _p value of Hammett" is defined as L. P. Proposed by Hammett, it quantifies the effect of substituents on the reaction rate or equilibrium of para-substituted benzene derivatives. Specifically, the following formula holds between the substituent in the para-substituted benzene derivative and the reaction rate constant or the equilibrium constant:
log (k / k ₀ ) = ρσ _p
Or log (K / K ₀ ) = ρσ _p
It is a constant (σ _p ) peculiar to the substituent in. In the above equation, k is the rate constant of the benzene derivative having no substituent, k ₀ is the rate constant of the benzene derivative substituted with the substituent, K is the equilibrium constant of the benzene derivative having no _{substituent, and K 0} is the substituent. The equilibrium constant of the benzene derivative substituted with, ρ represents the reaction constant determined by the type and conditions of the reaction. For a description of the “ _{hammet σ p} value” in the present invention and the numerical values of each substituent, see Hansch, C. et. Al. , Chem. Rev. , 91, 165-195 (1991) with respect to _{the σ p value.}

As an example of a partial structure containing a donor group and an acceptor group, a group represented by the following general formula (1a) or the following general formula (1b) can be mentioned.
General formula (1a)
A ¹ − D ¹ ― * ¹
General formula (1b)
D ^2- A ^2- * ²
In the general formulas (1a) and (1b), D ¹ and D ² each independently represent a donor group, and A ¹ and A ² each independently represent an acceptor group. * ¹ and * ² represent the linking position to the oxy group derived from the (meth) acryloyloxy group. The linking position may be linked to the oxy group with a single bond, or may be linked to the oxy group via a divalent linking group. For the description and preferable range of the divalent linking group, the description of "divalent linking group" in L of the following general formula (1) can be referred to.

Each donor group represented by D ¹ and D ² is preferably a group represented by the following general formula (ab1).

When the group represented by the general formula (ab1) is D ¹ of the general formula (1a), one of R ^{11 to} R ²⁰ is the connection position to the oxy group derived from the (meth) acryloyloxy group. Represents, and the rest of R ^{11 to} R ²⁰ independently represent hydrogen atoms or substituents. The linking position may be linked to the oxy group with a single bond or with a divalent linking group. For the description and preferable range of the divalent linking group, the description of "divalent linking group" for linking ^{the linking position * 1 of the general formula (1a) and the oxy group can be referred to.} The description of "divalent linking group" in L of the following general formula (1) can be referred to. The connection position of R ^{11 to} R ²⁰ is not particularly limited, but it is preferably any of ^{R 12 to} R ¹⁴ , and more preferably ^{R 13.} Further, ^{the number of substituents is not particularly limited in the rest except for the linking positions of R 11 to} R ²⁰ , and all of the remaining substituents may be unsubstituted (that is, hydrogen atoms). When ^{two or more of R 11 to} R ²⁰ are substituents, the plurality of substituents may be the same or different from each other. * Represents the binding position to the acceptor group.
When the group represented by the general formula (ab1) is D ² of the general formula (1b), R ^{11 to} R ²⁰ each independently represent a hydrogen atom or a substituent. The number of substituents among R ^{11 to} R ²⁰ is not particularly limited, and all of R ^{11 to} R ²⁰ may be unsubstituted (that is, hydrogen atoms). When ^{two or more of R 11 to} R ²⁰ are substituents, the plurality of substituents may be the same or different from each other. * Represents the binding position to the acceptor group.
Possible substituents of R ^{11 to} R ²⁰ include, for example, a hydroxy group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 alkyl substituted amino groups, 1 to 20 carbons aryl substituted amino groups, 6 to 40 carbons aryl groups, 3 to 40 carbons heteroaryl groups, 2 to 10 carbons alkenyl groups, 2 to 2 carbons Examples thereof include an alkynyl group of 10, an alkylamide group having 2 to 20 carbon atoms, an arylamide group having 7 to 21 carbon atoms, and a trialkylsilyl group having 3 to 20 carbon atoms. Of these specific examples, those substitutable by a substituent may be further substituted. More preferable substituents are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl substituted amino group having 1 to 20 carbon atoms, and an alkyl substituted amino group having 1 to 20 carbon atoms. It is an aryl-substituted amino group, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms.

R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ And R ²⁰ may be coupled to each other to form a cyclic structure. The cyclic structure may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a fused ring having two or more rings. The hetero atom referred to here is preferably one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the cyclic structure formed include a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an imidazoline ring, an oxazole ring, an isooxazole ring, a thiazole ring, and an iso. Examples thereof include a thiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and a cycloheptaene ring.

Among the groups represented by the general formula (ab1), R ¹⁵ and R ¹⁶ are not bonded to each other, R ¹⁵ and R ¹⁶ are bonded to each other in a single bond, or R ¹⁵ and R ^{16 are bonded to each other.} Are preferably bonded to each other to form a linking group having a linking chain length of 1 atom. When R ¹⁵ and R ¹⁶ are bonded to each other to form a linking group having a chain length of 1 atom, the cyclic structure formed as a result of the bonding of ^{R 15} and R ^{16 to each other is a 6-membered ring.} Specific examples of a linking group formed by bonding R ¹⁵ and R ¹⁶ to each other are represented by -O-, -S-, -N (R ⁹¹ )-or -C (R ⁹² ) (R ⁹³ )-. Linking groups can be mentioned. Here, R ^{91 to} R ⁹³ each independently represent a hydrogen atom or a substituent. Examples of the substituent that R ⁹¹ can take include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms. The ^{substituents that can be taken by R 92} and R ⁹³ are, independently, a hydroxy group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkylthio group having 1 to 20 carbon atoms. Alkyl-substituted amino groups having 1 to 20 carbon atoms, aryl-substituted amino groups having 1 to 20 carbon atoms, aryl groups having 6 to 40 carbon atoms, heteroaryl groups having 3 to 40 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, Examples thereof include an alkynyl group having 2 to 10 carbon atoms, an alkylamide group having 2 to 20 carbon atoms, an arylamide group having 7 to 21 carbon atoms, and a trialkylsilyl group having 3 to 20 carbon atoms.

As a preferable example of the group represented by the general formula (ab1), a group represented by any of the following general formulas (ab2) to (ab6) can be mentioned.

When the group represented by the general formulas (ab2) to (ab6) is D ¹ of the general formula (1a), one of R ^{21 to} R ²⁴ and R ^{27 to} R ³⁰ , R ^{31 to} R ^38. One of, one of R ^{41 to} R ⁴⁸ , one of R ^{51 to} R ⁵⁹ , and one of R ^{71 to} R ⁸⁰ are derived from (meth) acryloyloxy groups, respectively. It represents the position of connection to the oxy group, and the rest independently represent a hydrogen atom or a substituent. The connection position is preferably any of R ^{22 to} R ^{24 among R 21 to} R ²⁴ and R ^{27 to} R ^{30 , more preferably R 23} , and R ^{31 to} R ³⁸ . Of these, it is preferably any of ^{R 32 to} R ^{34 , more preferably R 33} , and of R ^{41 to} R ⁴⁸ , it is preferably any of ^{R 42 to} R ^{44 , and R 43} . Of R ^{51 to} R ⁵⁹ , it is preferably any of ^{R 52 to} R ^{54 , more preferably R 53} , and of R ^{71 to} R ⁸⁰ , R ^{72 to} R ^74. It is preferable that it is any of the above, and it is more preferable that it is ^{R 73.} When the group represented by the general formulas (ab2) to (ab6) is D ² of the general formula (1b), R ^{21 to} R ²⁴ , R ^{27 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to R. 59} , R ^{71 to} R ⁸⁰ each independently represent a hydrogen atom or a substituent. For the description of the linking position and the description of the substituent and the preferable range referred to here, the description of the linking position and the substituent that can be taken by ^{R 11 to} R ^{20 and the preferable range can be referred to.} * Represents the binding position to the acceptor group.
R ²¹ to R ²⁴ in ^{D 1, R 27 ~R 38,} R 41 ~R 48, after deducting what is coupling position ^{R 51 ~R 59, R 71 ~R} 80, and, R in the D ^{2 21} ~ R ²⁴ , R ²⁷ ~ R ³⁸ , R ⁴¹ ~ R ⁴⁸ , R ⁵¹ ~ R ⁵⁹ , R ⁷¹ ~ R ⁸⁰ are each independently represented by the above general formula (ab1), and R ¹⁵ and It is also preferable that R ¹⁶ is not bonded to each other and is a group represented by any of the above general formulas (ab2) to (ab6). ^{In particular, R 23} and R ²⁸ of the general formula (ab2) are groups represented by the above general formula (ab1), in which R ¹⁵ and R ¹⁶ are not bonded to each other, and the general formula (ab2). It is preferably a group represented by.
The number of substituents in R ^{21 to} R ²⁴ , R ^{27 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to} R ⁵⁹ , and R ^{71 to} R ^{80 is not particularly limited.} It is also preferable that all of them are unsubstituted (that is, hydrogen atoms) except for the connection position at D ^1. Further, when there are two or more substituents in each of the general formulas (ab2) to (ab6), the substituents may be the same or different. When a substituent is present in the general formulas (ab2) to (ab6), the substituent is preferably any of ^{R 22 to} R ²⁴ and R ^{27 to} R ^{29 in the case of the general formula (ab2).} , R ²³ and R ²⁸ , more preferably ^{any one of R 32 to} R ³⁷ for the general formula (ab3), and R ^{42 to R 42 for the general formula (ab4).} It is preferably any of R ⁴⁷ , and if it is the general formula (ab5), it is preferably any of R ⁵² , R ⁵³ , R ⁵⁶ , R ⁵⁷ , and R ⁵⁹ , and if it is the general formula (ab6). It is preferably any of R ^{72 to} R ⁷⁷ , R ⁷⁹ , and R ^{80. Further, R 79} and R ⁸⁰ of the general formula (ab6) are preferably substituted or unsubstituted alkyl groups, and more preferably substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.

In the general formulas (ab2) to (ab6), R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ , R ⁵⁴ and R ⁵⁹ , R ⁵⁵ and R ⁵⁹ , R ⁷¹ and R ⁷² , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , R ⁷⁹ and R ⁸⁰ may be coupled to each other to form an annular structure. For the description and preferred examples of the cyclic structure, in the above general formula (ab1), the description and preferred examples of the cyclic structure formed by bonding ^{R 11} and R ^{12 and the like to each other can be referred to.}

The acceptor group in A ¹ of the general formula (1a) and A ² of the general formula (1b) is a group represented by the following general formula (ab7) or a portion represented by the following general formula (ab7). It is preferably a group having a structure.

When the group represented by the general formula (ab7) is A ¹ of the general formula (1a), X ^{1 to} X ⁵ independently represent N or C (R ¹⁹ ), and R ¹⁹ is a hydrogen atom or a substitution. Represents a group. At ^{least one of X 1 to} X ⁵ is preferably N, more preferably 1 to 3 being N, and even more preferably 3 being N. * Represents the connection position to the donor group.
When the group represented by the general formula (ab7) is A ² of the general formula (1b), one of X ^{1 to} X ⁵ represents C (R ²⁰ ), and R ²⁰ is a (meth) acryloyloxy group. Represents the position of connection to an oxy group derived from, or a substituted or unsubstituted arylene group linked to the oxy group. The substituted or unsubstituted arylene group is preferably a substituted or unsubstituted phenylene group. The phenylene group may be any of a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group, but a 1,4-phenylene group is preferable. For the description and preferred range of the substituents that can be introduced into the arylene group, the preferred range of ^{the description of the substituents that R 19} can take can be referred to below. The linking position and the substituted or unsubstituted arylene group at R ²⁰ may be linked to the oxy group with a single bond or a divalent linking group. For the description and preferable range of the divalent linking group, the description of "divalent linking group" in L of the following general formula (1) can be referred to. The ^{rest of X 1 to} X ⁵ , except for C (R ²⁰ ), independently represent N or C (R ¹⁹ ), where R ¹⁹ represents a hydrogen atom or a substituent. * Represents the connection position to the donor group. At ^{least one of X 1 to} X ⁵ is preferably N, more preferably 1 to 3 being N, and even more preferably 3 being N.
When the groups represented by the general formula (ab7) has a plurality of R ^19, a plurality of R ¹⁹ may be the being the same or different. Examples of the substituent that R ¹⁹ can take include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a cyano group, a halogen atom, and a heteroaryl group having 5 to 40 carbon atoms. It is preferably an aryl group having 6 to 40 carbon atoms. Of these substituents, those substitutable by the substituent may be substituted.

A structure in which the structure represented by the general formula (ab7) is bonded to the linking group can also be adopted as the acceptor group. The "linking group" here means a linking group that links the binding position * of the general formula (ab7) and the donor group. In that case, as the linking group, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group is preferable, a substituted or unsubstituted arylene group is more preferable, and a substituted or unsubstituted phenylene group is used. It is more preferable to have. The phenylene group may be any of a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group, but a 1,4-phenylene group is preferable. For the description and preferred range of the substituents that can be introduced into the arylene group and the heteroarylene group, the preferred range of the description of the substituents that ^{R 19 can take can be referred to.}

As a preferable example of the group represented by the general formula (ab7), a group represented by the following formula (ab8) can be mentioned.

One of the hydrogen atoms in formula (ab8) is substituted with a donor group. When the group represented by the formula (ab8) is A ² of the general formula (1b), the other hydrogen atom in the formula (ab8) is an oxy group derived from the (meth) acryloyloxy group, or an oxy group. The oxy group is substituted with a divalent linking group that links the group represented by the general formula (ab8). The remaining hydrogen atom in the formula (ab8) may be substituted with a substituent or may be unsubstituted.

As ^{an example of each acceptor group represented by A 1} and A ² , a group represented by the following formula (ab9) can also be mentioned.

One of the hydrogen atoms in formula (ab9) is substituted with a donor group. When the group represented by the formula (ab9) is A ² of the general formula (1b), the other hydrogen atom in the formula (ab9) is an oxy group derived from the (meth) acryloyloxy group, or an oxy group. The oxy group is substituted with a divalent linking group that links the group represented by the general formula (ab8). The remaining hydrogen atom in the formula (ab9) may be substituted with a substituent or may be unsubstituted. For the description and preferable range of the divalent linking group, the description of "divalent linking group" in L of the following general formula (1) can be referred to.

In the following, examples of delayed fluorescent compounds that can be introduced into acrylic polymers as TADF structures will be given. These delayed fluorescent substances are introduced into acrylic polymers by substituting one hydrogen atom with an oxy group derived from a (meth) acryloyloxy group or a divalent linking group that links the oxy group with the delayed fluorescent group. Will be done. The remaining hydrogen atoms of the delayed fluorescent substance may be substituted with a substituent or may be unsubstituted. For the description and preferable range of the divalent linking group, the description of "divalent linking group" in L of the following general formula (1) can be referred to.

Of these, the ones that are particularly preferable are the residues of the delayed fluorescent substance represented by the following formula.
[In each equation, * represents the position of connection to L in the general equation (1). The hydrogen atom in the formula may be substituted with a substituent. ]

As preferred delayed phosphors, paragraphs 0008 to 0048 and 0995 to 0133 of WO 2013/154604, paragraphs 0007 to 0047 and 0073 to 985 of WO 2013/011954, and paragraphs 0007 to 0033 and 0059 to 0066 of WO 2013/011955. , WO 2013/081088, paragraphs 0008 to 0071 and 0118 to 0133, Japanese Patent Application Laid-Open No. 2013-256490, paragraphs 0009 to 0046 and 093 to 0134, Japanese Patent Application Laid-Open No. 2013-116975, paragraphs 0008 to 0020 and 0038 to 0040. Paragraphs 0007 to 0032 and 0079 to 0084 of WO2013 / 133359, paragraphs 0008 to 0054 and 0101 to 0121 of WO2013 / 161437, paragraphs 0007 to 0041 and 0060 to 0069 of JP2014-9352, JP2014. Examples of compounds included in the general formulas described in paragraphs 0008 to 0048 and 0067 to 0076 of JP-9224, particularly exemplary compounds, which emit delayed fluorescence. In addition, JP2013-253121A, WO2013 / 133359A, WO2014 / 034535, WO2014 / 115743, WO2014 / 122895, WO2014 / 126200, WO2014 / 136758, WO2014 / 133121. WO2014 / 136860, WO2014 / 196585, WO2014 / 189122, WO2014 / 168101, WO2015 / 008580, WO2014 / 203840, WO2015 / 002213, WO2015 / 016200, WO2015 / 019725, WO2015 / 072470, WO2015 / 108049, WO2015 / 080182, WO2015 / 072537, WO2015 / 080183, JP2015-129240, WO2015 / 129714, Described in WO2015 / 129715, WO2015 / 133501, WO2015 / 136880, WO2015 / 137244, WO2015 / 137202, WO2015 / 137136, WO2015 / 146541, WO2015 / 159541. A light emitting material that emits delayed fluorescence can also be preferably adopted. The above publications described in this paragraph are cited herein as part of this specification.

The delayed fluorescent substance used as the TADF structure _{preferably has a ΔE ST} difference between the _{lowest excited singlet energy level E S1} and the lowest excited triplet energy level E _T1 of 0.3 eV or less, preferably 0.2 eV or less. More preferably, it is more preferably 0.1 eV or less, and even more preferably 0.05 eV or less. Method of measuring the E _S1, E _T1 and Delta] E _ST, can be referred to in the column (E _S1, E _T1, the measurement method of Delta] E _ST).

As a preferable example of the TADF-containing structural unit constituting the acrylic polymer of the present invention, a structural unit represented by the following general formula (1) can be mentioned.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group.
DF represents a group that can emit delayed fluorescence. As the group capable of emitting delayed fluorescence represented by DF, the above-mentioned TADF structure "partial structure including the main structure of delayed fluorescence" or "partial structure including donor group and acceptor group" can be adopted. it can. For their description, preferred range, and specific examples, see the above-mentioned "partial structure including the main structure of delayed fluorescent substance" and "partial structure containing donor group and acceptor group", general formula (1a) or general formula (1a). The description of the group represented by 1b), the preferred range, and specific examples can be referred to.
L represents a single bond or a divalent linking group. The "divalent linking group" in L preferably has a structure represented by the following general formula (1c).
General formula (1c)
* ³ − (CH ₂ ) _n1 − L ^1c − (CH ₂ ) _n2 − * ⁴
In the general formula (1c), n1 and n2 each independently represent an integer of 0 to 10. L ^1c represents an alkylene group (-(CH ₂ )-), an oxycarbonyl group (-COO-) or an iminocarbonyloxy group (-OCONH-). * ³ represents the bond position to DF, and * ⁴ represents the bond position to the oxy group derived from the oxy (meth) acryloyl group.
From the viewpoint of forming a stable amorphous film, n1 is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 to 2. Further, n2 is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 to 2.

When the acrylic polymer of the present invention contains two or more TADF-containing structural units, the plurality of TADF-containing structural units may be the same or different from each other. Further, all of the structural units constituting the acrylic polymer of the present invention may be TADF-containing structural units, or may include TADF-free structural units in addition to TADF-containing structural units. In other words, the acrylic polymer of the present invention may be a homopolymer or a copolymer of a TADF-containing monomer, or may be a copolymer of a TADF-containing monomer and a TADF-free monomer.

As a preferable example of the acrylic polymer of the present invention, an acrylic polymer represented by the following general formula (2) can be mentioned. The following general formula (2) includes a homopolymer of a structural unit having DF in the side chain, and a copolymer containing two or more structural units having DF in the side chain and not containing a structural unit having ^{R 3 in the side chain.} , A general formula for an acrylic polymer comprising a copolymer of a structural unit having DF in the side chain and a structural unit having R ^{3 in the side chain.} Each structural unit of the copolymer of the structural unit having DF in the side chain and the structural unit having R ³ in the side chain may be one kind or two or more kinds, respectively.

In the general formula (2), R ¹ , DF and L are ^{synonymous with R 1} , DF and L in the general formula (1). ¹ , DF and L can be referred to.
R ² represents a hydrogen atom or a methyl group, and R ³ represents a substituted or unsubstituted alkyl group. The alkyl group in R ³ may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 10 from the viewpoint of forming a stable amorphous film. The substituent that can be introduced into the alkyl group is a substituent that does not contain a TADF structure, and examples thereof include an isopropyl group, a cyclohexyl group, and an adamantyl group.
In the acrylic polymer represented by the general formula (2), the structural unit having DF in the side chain corresponds to the TADF-containing structural unit, and the structural unit having ^{R 3 in the side chain corresponds to the TADF-free structural unit.} In the present specification, the general formula (3) representing the structural unit having ^{R 3 in the side chain shown here may be referred to as the general formula (3).}
In the general formula (2), m represents the ratio of TADF-containing structural units when all the structural units constituting the acrylic polymer are 100, and l is when all the structural units constituting the acrylic polymer are 100. Represents the proportion of TADF-free constituent units. n represents the magnification of the actual number of constituent units of the acrylic polymer with respect to 100. m is preferably 0.1 or more, more preferably 1 or more, and even more preferably 5 or more. The ratio m of the TADF-containing structural unit and the ratio l of the TADF-free structural unit in the acrylic polymer can be determined by NMR analysis of the target acrylic polymer. For example, when the TADF-free structural unit contains a methyl group and the TADF-containing structural unit contains an aromatic ring, the integrated value a (equivalent to 3H) of the peak belonging to the proton of the methyl group of the TADF-free structural unit is used. From the integrated value b (corresponding to 6H minutes) of the peak attributed to the aromatic proton of the TADF-containing constituent unit, l and m can be obtained by the following formula.
l = (100 × 2 × a) / (2 × a + b) Equation (I)
m = 100-l formula (II)
In formula (I), a indicates the integrated value of the NMR peak attributed to the proton of the methyl group, and b indicates the integrated value of the NMR peak attributed to the specific aromatic ring proton.

Here, it is generally said that it is preferable that the acrylic polymer has a large molecular weight, but if the molecular weight is too large, problems such as difficulty in dissolving occur. On the other hand, the molecular weight of the acrylic polymer of the present invention is not particularly limited, and the weight average molecular weight Mw and the number average molecular weight Mn are appropriately controlled by a size exclusion chromatography (SEC) method, for example, Waters' Alliance e2695. It can be measured by the system, 2414 differential refractometer.

Hereinafter, specific examples of the acrylic polymer of the present invention will be illustrated. However, the acrylic polymer of the present invention should not be construed as limited by these specific examples.

Although the embodiment of the acrylic polymer of the present invention has been described above, the composition of the acrylic polymer of the present invention is not limited thereto. For example, the acrylic polymer of the present invention may be a copolymer using a radically polymerizable monomer other than the acrylic monomer as a substrate in addition to the acrylic monomer. Further, as the monomer having a (meth) acryloyloxy group, a monofunctional one or a polyfunctional one may be used so that a crosslinked structure is formed between the polymer chains.

(Measurement method of _{E S1} , E _T1 , ΔE _{ST)
For "ΔE ST} " in the present specification, the lowest excited singlet energy level ( _ES1 ) and the lowest triplet energy level ( _ET1 ) are calculated by the following method, and ΔE _ST = E _S1- E _T1. This is the required value. If there is a document value, a simple study or consideration may be performed using the document value.
(1) Lowest excited singlet energy level E _S1
A sample is prepared by dissolving the compound to be measured in toluene at ^{a concentration of 10 -4} M or 10 ^-5 M, and the fluorescence spectrum of this sample is measured at room temperature (300 K). The fluorescence spectrum of this sample is measured at room temperature (300K). Specifically, by integrating the light emission from immediately after the excitation light is incident to 100 nanoseconds after the incident, a fluorescence spectrum having the emission intensity on the vertical axis and the wavelength on the horizontal axis is obtained. A tangent line is drawn with respect to the rising edge of the fluorescence spectrum on the short wavelength side, and the wavelength value λedge [nm] at the intersection of the tangent line and the horizontal axis is obtained. _{Let E S1} be a value obtained by converting this wavelength value into an energy value using the following conversion formula.
Conversion _{formula: E S1 [eV] = 1239.85} / λedge
The emission spectrum can be measured by using, for example, a fluorescence spectrophotometer (FluoroMax Plus, manufactured by Horiba, Ltd.).
(2) Lowest excited triplet energy level E _T1
The same sample used for the measurement of the lowest excited singlet energy level E _S1 is cooled to 77K, the sample for phosphorescence measurement is irradiated with excitation light, and the phosphorescence intensity is measured using a spectrophotometer. Specifically, by integrating the light emission 100 milliseconds after the excitation light is incident, a phosphorescent spectrum having the vertical axis as the light emission intensity and the horizontal axis as the wavelength is obtained. A tangent line is drawn with respect to the rising edge of the phosphorescent spectrum on the short wavelength side, and the wavelength value λedge [nm] at the intersection of the tangent line and the horizontal axis is obtained. The value converted to the energy value conversion equation shown below the wavelength value and E _T1.
Conversion formula: E _T1 [eV] = 1239.85 / λedge
The tangent to the rising edge of the phosphorescent spectrum on the short wavelength side is drawn as follows. First, when moving on the spectrum curve from the short wavelength side of the phosphorescent spectrum to the maximum value on the shortest wavelength side of the maximum values of the spectrum, consider the tangents at each point on the curve toward the long wavelength side. .. This tangent increases in slope as the curve rises (ie, as the vertical axis increases). The tangent line drawn at the point where the value of the slope reaches the maximum value is defined as the tangent line with respect to the rising edge of the phosphorescent spectrum on the short wavelength side.
The maximum point having a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above, and the slope value closest to the maximum value on the shortest wavelength side is the maximum. The tangent line drawn at the point where the value is taken is taken as the tangent line to the rising edge of the phosphorescent spectrum on the short wavelength side.

<Acrylic polymer synthesis method>
The acrylic polymer of the present invention is a polymerization reaction of an acrylic monomer having a TADF structure (TADF-containing monomer), or an acrylic monomer having a TADF structure (TADF-containing monomer) and an acrylic monomer not containing a TADF structure (TADF-free monomer). It can be synthesized by a polymerization reaction.
As an example of the TADF-containing monomer used for the synthesis of the acrylic polymer represented by the general formula (2), the acrylic monomer represented by the following general formula (4) can be mentioned.

In the general formula (4), R ¹ , DF and L are ^{synonymous with R 1} , DF and L in the general formula (1). ¹ , DF and L can be referred to.

As an example of the TADF-free monomer, an acrylic monomer represented by the following general formula (5) can be mentioned.

In the general formula (5), R ² and R ^3, the general formula (2) have the same meanings as R ² and R ³ in the description and the preferred range and specific examples, R ² and in the general formula (2) The description for R ³ can be referred to.
The acrylic polymer represented by the general formula (2) having m of 100 is a copolymer of one monomer selected from the monomer group represented by the general formula (4) above, or a homopolymer of one monomer. It can be obtained as a copolymer of two or more monomers selected from this monomer group. Further, the acrylic polymer represented by the general formula (2) having m less than 100 (l is more than 0) is one or more selected from the monomer group represented by the general formula (4). Can be obtained as a copolymer of the above-mentioned monomer and one or more monomers selected from the group of monomers represented by the following general formula (5).
In the polymerization reaction, known polymerization conditions of the acrylic monomer can be appropriately selected and used. For details of the polymerization reaction, a synthetic example described later can be referred to.

In the following, examples of compounds of the monomers represented by the general formula (4) used in the synthesis of the acrylic polymer of the present invention will be illustrated. However, the TADF-containing monomer used in the synthesis of the acrylic polymer of the present invention should not be construed as limited by these specific examples. Further, as a specific example of the TADF-free monomer, methyl methacrylate will be exemplified.

<Luminescent material>
Next, the light emitting material of the present invention will be described.
The light emitting material of the present invention is characterized by containing the acrylic polymer of the present invention.
For a description of the acrylic polymer of the present invention, a preferable range, and specific examples, the description in the <Acrylic polymer> column can be referred to.
The acrylic polymer of the present invention emits delayed fluorescence, in other words, when it causes an intersystem crossing from an excited triplet state to an excited singlet state and is deactivated from the excited singlet state. It can emit light. Therefore, in the acrylic polymer of the present invention, the excited triplet energy, which is non-radiatively deactivated by a normal fluorescent material, can be effectively used for light emission, and high luminous efficiency can be obtained. Further, the acrylic polymer of the present invention shows high solubility in many organic solvents, and the ratio of the structural unit containing the TADF structure to the structural unit not containing the TADF structure (m and l in the general formula (2)). By controlling this, it exhibits good solubility in non-halogen organic solvents such as acetone and ethyl acetate, which are poorly soluble in non-polymerized delayed fluorescent substances. Therefore, the acrylic polymer of the present invention can easily form a film by a coating method while suppressing the environmental load to a low level, whereby a high-quality amorphous film can be formed at low cost. Further, the acrylic polymer of the present invention tends to have a high glass transition temperature, and by appropriately selecting the ratio of the TADF structure, the linking group, the side chain of the TADF-free constituent unit, etc., the glass transition temperature is high over 120 ° C. It can have a temperature. Therefore, the amorphous film formed of the acrylic polymer of the present invention exhibits high thermal stability. Furthermore, the acrylic polymer of the present invention exhibits high luminous efficiency even as a single film, and can eliminate the host material normally required for delayed fluorescent materials. As a result, the manufacturing process of the element can be further simplified, crystallization and phase separation of the film, which are problems in the multi-component coating film, can be avoided, and the stability of the amorphous film can be further improved. Can be improved.
From the above, the acrylic polymer of the present invention is useful as a light emitting material, and can be particularly effectively used as a material for a light emitting layer of an organic light emitting device.

<Membrane>
Next, the film of the present invention will be described.
The film of the present invention is a film containing the acrylic polymer of the present invention.
For a description of the acrylic polymer of the present invention, a preferable range, and specific examples, the description in the <Acrylic polymer> column can be referred to.
The film of the present invention is preferably a coating film containing the acrylic polymer of the present invention. Here, the "coating film" refers to a film formed by applying and drying a liquid material containing an acrylic polymer. In the coating film forming step, other treatments such as heat treatment may be performed if necessary.
Further, the film of the present invention is preferably an amorphous film, and more preferably an amorphous film formed by a coating method. Here, the "amorphous film" may be entirely amorphous or may have a crystal structure in a part thereof. The fact that the film is an amorphous film can be determined by observing the glass transition temperature. The glass transition temperature of the film is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 115 ° C. or higher, and particularly preferably 120 ° C. or higher. The glass transition temperature of the coating film can be measured by the differential scanning calorimetry method.
The acrylic polymer of the present invention exhibits high solubility in many organic solvents and can have a glass transition temperature of more than 120 ° C. Therefore, it is a good quality amorphous polymer having high thermal stability depending on the coating method. It can be formed as a film. Therefore, the film of the present invention can be preferably used as an organic film of an organic light emitting device, and further, since the acrylic polymer of the present invention exhibits high luminous efficiency, it can be suitably used as a light emitting layer of an organic light emitting device.
The content of the acrylic polymer contained in the film of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, and further preferably 5% by weight or more.

<Organic light emitting element>
As described above, the acrylic polymer of the present invention exhibits high luminous efficiency, and an amorphous film having high stability can be formed by a coating method. Therefore, by using the acrylic polymer of the present invention as a material for an organic photoluminescence element (organic PL element) or an organic electroluminescence element (organic EL element), it is possible to provide an organic light emitting element having high luminous efficiency at low cost. it can.
The organic photoluminescence device has a structure in which at least a light emitting layer is formed on a substrate. The organic electroluminescence device has at least an anode, a cathode, and a structure in which an organic layer is formed between the anode and the cathode. The organic layer includes at least a light emitting layer, and may be composed of only a light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer, and the like. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. A specific structural example of the organic electroluminescence device is shown in FIG. In FIG. 3, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode.
Hereinafter, each member and each layer of the organic electroluminescence device will be described. The description of the substrate and the light emitting layer also applies to the substrate and the light emitting layer of the organic photoluminescence device.

(substrate)
The organic electroluminescence device of the present invention is preferably supported by a substrate. The substrate is not particularly limited as long as it is conventionally used for organic electroluminescence devices, and for example, a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.

(anode)
As the anode in the organic electroluminescence element, a metal having a large work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as _{CuI, indium zinc oxide (ITO), SnO 2, and ZnO.} Further, a material such as IDIXO (In ₂ O _3- ZnO) which is amorphous and can produce a transparent conductive film may be used. For the anode, a thin film may be formed by forming a thin film of these electrode materials by a method such as thin film deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not required so much (about 100 μm or more). ), A pattern may be formed through a mask having a desired shape during vapor deposition or sputtering of the electrode material. Alternatively, when a coatable material such as an organic conductive compound is used, a wet film forming method such as a printing method or a coating method can also be used. When light emission is taken out from this anode, it is desirable to increase the transmittance to more than 10%, and the sheet resistance as the anode is preferably several hundred Ω / cm ² or less. Further, the film thickness depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(cathode)
On the other hand, as the cathode, a metal having a small work function (4 eV or less) (referred to as an electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O). ₃ ) Examples include mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron injectability and durability against oxidation and the like, a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture. Magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture, aluminum and the like are suitable. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance of the cathode ^{is preferably several hundred Ω / cm 2} or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. Since the emitted light is transmitted, it is convenient that the emission brightness is improved if either the anode or the cathode of the organic electroluminescence element is transparent or translucent.
Further, by using the conductive transparent material mentioned in the description of the anode for the cathode, a transparent or translucent cathode can be produced, and by applying this, an element in which both the anode and the cathode have transparency can be obtained. Can be made.

(Light emitting layer)
The light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from the anode and the cathode, respectively. As the luminescent material, one or more selected from the acrylic polymer group of the present invention can be used. A host material may be used for the light emitting layer in addition to the light emitting material, but it is preferable not to use the host material. By not using the host material, when the light emitting layer of the acrylic polymer is formed by the coating method, phase separation and crystallization of the coating film are suppressed, and a highly stable and high quality amorphous light emitting layer can be formed. .. On the other hand, when the host material is used, the singlet excitons and triplet excitons generated in the light emitting material can be confined in the light emitting material, whereby the luminous efficiency can be improved. As the host material, it is preferable to use a material in which at least one of the excited singlet energy level and the excited triplet energy level is higher than that of the light emitting material, and both the excited singlet energy level and the excited triplet energy level are used. It is more preferable to use a material having a higher value than that of the light emitting material. In the organic light emitting device or the organic electroluminescence device of the present invention, the light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This emission includes both fluorescent and delayed fluorescence.
The content of the acrylic polymer in the light emitting layer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and further preferably 5% by weight or more.

(Injection layer)
The injection layer is a layer provided between the electrode and the organic layer in order to reduce the driving voltage and improve the emission brightness. There are a hole injection layer and an electron injection layer, and between the anode and the light emitting layer or the hole transport layer, And may be present between the cathode and the light emitting layer or the electron transporting layer. The injection layer can be provided as needed.

(Blocking layer)
The blocking layer is a layer capable of blocking the diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer. The electron blocking layer can be arranged between the light emitting layer and the hole transporting layer to prevent electrons from passing through the light emitting layer toward the hole transporting layer. Similarly, the hole blocking layer can be placed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer towards the electron transporting layer. The blocking layer can also be used to prevent excitons from diffusing outside the light emitting layer. That is, the electron blocking layer and the hole blocking layer can also function as exciton blocking layers, respectively. The electron blocking layer or exciton blocking layer referred to in the present specification is used in the sense that one layer includes a layer having the functions of an electron blocking layer and an exciton blocking layer.

(Hole blocking layer)
The hole blocking layer has a function of an electron transporting layer in a broad sense. The hole blocking layer has a role of blocking the holes from reaching the electron transporting layer while transporting electrons, which can improve the recombination probability of electrons and holes in the light emitting layer. As the material of the hole blocking layer, a material of the electron transport layer described later can be used as needed.

(Electronic blocking layer)
The electron blocking layer has a function of transporting holes in a broad sense. The electron blocking layer has a role of blocking electrons from reaching the hole transporting layer while transporting holes, which can improve the probability that electrons and holes are recombined in the light emitting layer. ..

(Exciton blocking layer)
The exciton blocking layer is a layer for preventing excitons generated by the recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer, and the excitons are inserted by inserting this layer. It is possible to efficiently confine it in the light emitting layer, and it is possible to improve the light emitting efficiency of the element. The exciton blocking layer can be inserted into either the anode side or the cathode side adjacent to the light emitting layer, and both can be inserted at the same time. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted between the hole transport layer and the light emitting layer adjacent to the light emitting layer, and when inserted on the cathode side, the light emitting layer and electrons can be inserted. The layer can be inserted adjacent to the light emitting layer between the transport layer and the light emitting layer. Further, a hole injection layer, a hole transport layer, an electron blocking layer and the like can be provided between the anode and the exciton blocking layer adjacent to the exciton blocking layer of the light emitting layer, and the cathode and the light emitting layer can be provided. An electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided between the exciton blocking layer adjacent to the cathode side. When the blocking layer is arranged, it is preferable that at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is higher than the excited singlet energy and the excited triplet energy of the light emitting material.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer may be provided with a single layer or a plurality of layers.
The hole transporting material has either injection or transport of holes or an electron barrier property, and may be either an organic substance or an inorganic substance. Known hole transporting materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, etc. Amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilben derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, especially thiophene oligomers, etc. It is preferable to use a group tertiary amine compound and a styrylamine compound, and it is more preferable to use an aromatic tertiary amine compound.

(Electronic transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer may be provided with a single layer or a plurality of layers.
The electron transporting material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer. Examples of the electron transporting layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, freolenidenemethane derivatives, anthracinodimethane and anthrone derivatives, and oxadiazole derivatives. Further, among the above oxadiazole derivatives, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is replaced with a sulfur atom, and a quinoxalin derivative having a quinoxalin ring known as an electron-withdrawing group can also be used as an electron transport material. Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

The film forming method of each layer constituting the organic electroluminescence element is not particularly limited and may be produced by either a dry process or a wet process, but the layer containing the acrylic polymer of the present invention is a wet process such as a spin coating method. It is preferable to prepare with.

Hereinafter, preferable materials that can be used for the organic electroluminescence device will be specifically exemplified. However, the materials that can be used in the present invention are not limitedly interpreted by the following exemplary compounds. Further, even a compound exemplified as a material having a specific function can be diverted as a material having another function.

First, as the host material of the light emitting layer, a sufficiently high luminous efficiency can be obtained without using it in the present invention, but it can also be used. The compounds that can be used as host materials are listed below.

Next, examples of preferable compounds that can be used as the hole injection material will be given.

Next, examples of preferable compounds that can be used as a hole transport material will be given.

Next, examples of preferable compounds that can be used as an electron blocking material are given.

Next, examples of preferable compounds that can be used as a hole blocking material are given.

Next, examples of preferable compounds that can be used as an electron transport material will be given.

Next, examples of preferable compounds that can be used as an electron injection material will be given.

Examples of preferable compounds as materials that can be further added are given. For example, it may be added as a stabilizing material.

The organic electroluminescence device produced by the above method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by the excitation triplet energy, the wavelength corresponding to the energy level is confirmed as phosphorescent light. In the case of light emission by excitation singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. Further, since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence emission, the emission lifetime can be distinguished by fluorescence and delayed fluorescence.

The organic electroluminescence device can be applied to any of a single device, a device having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, by forming a light emitting layer by a coating method using the acrylic polymer of the present invention, it is possible to provide an organic light emitting device having greatly improved luminous efficiency at low cost. The organic light emitting device such as the organic electroluminescence device using the acrylic polymer of the present invention can be further applied to various applications. For example, it is possible to manufacture an organic electroluminescence display device using this organic electroluminescence element. For details, refer to "Organic EL Display" (Ohmsha) co-authored by Shizushi Tokito, Chihaya Adachi, and Hideyuki Murata. You can refer to it. In particular, this organic electroluminescence device can also be applied to organic electroluminescence lighting and backlights, which are in great demand.

The features of the present invention will be described in more detail with reference to Examples below. The materials, treatment contents, treatment procedures, etc. shown below can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the specific examples shown below. The emission characteristics are evaluated by a spectrophotometer (Horiba Seisakusho Co., Ltd., FluoroMax Plus), a source meter (Caseley Co., Ltd .: 2400 series), an external quantum efficiency measuring device (Hamamatsu Photonics Co., Ltd., C9920-12), and an absolute quantum. This was performed using a yield measuring device (Hamamatsu Photonics Co., Ltd., C9920-02) and a small fluorescence lifetime measuring device (Hamamatsu Photonics Co., Ltd., C11367-21).
In this example, the unit ratio of the acrylic polymer was calculated by measuring the NMR spectrum of the target acrylic polymer and using the following formula from the integrated value of a specific NMR peak.
l = (100 × 2 × a) / (2 × a + b)
m = 100-l
In the formula, l indicates the ratio of structural units (methyl methacrylate units) derived from methyl methacrylate when the total number of structural units is 100, and m is the ratio of TADF-containing structural units when the total number of structural units is 100. Is shown. a represents the integrated value of the NMR peak (around 3.6 ppm) attributed to the proton of the methyl group of the methyl methacrylate unit, and corresponds to three protons. b shows the integrated value of the NMR peak (8.7 ppm to 9.1 ppm) attributed to the aromatic protons of the TADF-containing constituent unit, and corresponds to 6 protons. The NMR spectrum was measured using ECA600 manufactured by JASCO Corporation.
The weight average molecular weight Mw and the number average molecular weight Mn of the acrylic polymer were measured by the size exclusion chromatography (SEC) method (Waters alliance e2695 system, 2414 differential refractometer).

(Example 1) Synthesis and evaluation of acrylic polymer In this example, an acrylic monomer having a TADF structure was synthesized, and the physical properties of the acrylic polymer synthesized using the monomer were evaluated.
[A] Monomer synthesis 1
As shown below, here, the intermediates A1 and A2 are synthesized, the monomer 1-MA and the monomer 1-NEMA (TADF-containing monomer) are synthesized from the intermediate A1, and the monomer 1-EMA (TADF) is synthesized from the intermediate A2. Containing monomer) was synthesized.

(A-1) Synthesis Steps of Intermediates A1 and A2 Intermediates A1 and A2 were synthesized by the following synthetic route. In the reaction formula below, TBS represents a t-butyldimethylsilyl group.

Synthetic of Intermediate a1 Under an argon atmosphere, 3- (4-bromophenyl) -1-propanol (5.00 g, 23.2 mmol) and imidazole (2.37 g, 34.9 mmol, 1.50 eq) were added to N, N. -Dissolved in dimethylformamide (super dehydrated grade, 50 mL, 10 v / w times) and cooled to 5 ° C. or lower. To this mixture was gradually added t-butyldimethylsilyl chloride (5.26 g, 34.9 mmol, 1.50 eq) and stirred for 5 minutes, and further stirred at 20-30 ° C. for 3 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/2), it was confirmed that the raw materials had disappeared. A saturated aqueous solution of ammonium chloride (80 mL, 16.0 v / w times) and n-hexane (100 mL, 20.0 v / w times) were added to this reaction solution to separate the layers, and the organic layer was dried over anhydrous magnesium sulfate. After that, it was concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/49 was used as the eluent, and the concentrated residue was subjected to column chromatography (silica gel: Wakosil C-300 (75.0 g, 15.0 w / w times)). By purification, a pale yellow oil of intermediate a1 was obtained in a yield of 7.33 g and a yield of 95.7%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 7.39 (d, 2H), 7.06 (d, 2H), 3.61 (t, 2H), 2.63 (t, 2H) ), 1.82-1.77 (m, 2H), 0.90 (s, 9H), 0.05 (s, 6H)

Synthetic bis (dibenzylideneacetone) palladium (0) (157 mg, 0.27 mmol, 0.03 eq), (±) -binap (255 mg, 0.41 mmol, 0.045 eq), and sodium t-butoxide (255 mg, 0.41 mmol, 0.045 eq) of intermediate a2. 1.31 g, 13.7 mmol, 1.50 eq) was placed in a Schlenk tube and replaced with argon. To this mixture, 2-isopropenylaniline (1.33 g, 10.0 mmol, 1.10 eq), intermediate a1 (3.00 g, 9.1 mmol), and xylene (dehydrated grade, 21 mL, 7.10 eq) under argon airflow. (0v / w times) was added, and the mixture was stirred at an outside temperature of 145 ° C. for 6 hours under a light-shielded airtightness. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/19), it was confirmed that the raw materials were almost eliminated. This reaction solution was cooled to 50 ° C. or lower, and water (50 mL, 16.7 v / w times amount) and toluene (10 mL, 3.3 v / w times amount) were added to separate the liquids (first liquid separation). Toluene (30 mL, 10.0 v / w times) is added to the lower layer and the liquid is separated (second liquid separation), and the upper layer (organic layer) obtained by the first liquid separation and the second liquid separation are obtained. The upper layer (organic layer) was combined and washed with saturated brine (30 mL, 10.0 v / w times). The washed organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/19 was used as the eluent, and the concentrated residue was subjected to column chromatography (silica gel: Wakosil C-300 (75.0 g, 25.0 w / w times)). After purification, a pale yellow oil of intermediate a2 was obtained in a yield of 3.25 g and a yield of 93.7%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 7.25 (d, 1H), 7.15-7.09 (m, 4H), 7.01 (d, 2H), 6.86 (T, 1H), 5.81 (s, 1H), 5.30 (s, 1H), 5.07 (s, 1H), 3.64 (t, 2H), 2.62 (t, 2H) , 2.07 (s, 3H), 1.84-1.80 (m, 2H), 0.91 (s, 9H), 0.06 (s, 6H)

Synthesis of Intermediate a3 Intermediate a2 (16.20 g, 42.9 mmol) was dissolved in phosphoric acid (85%) (191.0 g, 11.8 w / w times), and the internal temperature was 20 to 30 ° C. under shading. Was stirred for 16 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/1), it was confirmed that the raw materials were almost eliminated. To this reaction solution, 30% potassium hydroxide (600 g, 37.0 w / w times amount) was added while keeping the internal temperature at 40 ° C. or lower, and the solution was separated with toluene (240 mL, 14.8 v / w times amount) (1). Second separation). Toluene (80 mL, 4.9 v / w times) is added to the lower layer and the liquid is separated (second liquid separation), and the upper layer (organic layer) obtained by the first liquid separation and the second liquid separation are obtained. The upper layer (organic layer) was combined and washed in the order of saturated aqueous sodium hydrogen carbonate solution (160 mL, 9.9 v / w times) and saturated saline (160 mL, 9.9 v / w times). The washed organic layer was dried over anhydrous sodium sulfate, and then concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 3/7 was used as the eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (240 g, 14.8 w / w times)). , The yellow oil of intermediate a3 was obtained in a yield of 10.33 g and a yield of 91.0%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 7.38 (d, 1H), 7.21 (s, 1H), 7.12-7.09 (m, 1H), 6.96 -6.90 (m, 2H), 6.69 (d, 1H), 6.65 (d, 1H), 6.10 (s, 1H), 3.72-3.69 (m, 2H), 2.68 (t, 2H), 1.92-1.87 (m, 2H), 1.58 (s, 6H)

Synthesis of Intermediate a4 Under light-shielded and argon atmosphere, Intermediate a3 (10.27 g, 38.4 mmol) and imidazole (3.92 g, 57.6 mmol, 1.50 eq) are mixed with dichloromethane (dehydration grade, 92 mL, 9 v / w). It was dissolved in (double amount) and cooled to 5 ° C. or lower. T-Butyldimethylsilyl chloride (6.37 g, 42.3 mmol, 1.10 eq) was gradually added to the mixture, and the mixture was further stirred at 20 to 30 ° C. for 17 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/1), it was confirmed that the raw materials had disappeared. Chloroform (200 mL, 19.5 v / w times) and water (160 mL, 15.6 v / w times) are added to this reaction solution to separate the layers, and the organic layer is separated by saturated brine (160 mL, 15.6 v / w). After washing with (w times the amount) and drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/19 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (205 g, 20.0 w / w times)). , The yellow oil of intermediate a4 was obtained in a yield of 13.78 g and a yield of 94.0%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 7.37 (d, 1H), 7.18 (s, 1H), 7.10-7.07 (m, 1H), 6.93 -6.88 (m, 2H), 6.68 (d, 1H), 6.62 (d, 1H), 6.07 (s, 1H), 3.64 (t, 2H), 2.62 ( t, 2H), 1.84-1.79 (m, 2H), 1.57 (s, 6H), 0.91 (s, 9H), 0.06 (s, 6H)

Synthesis of Intermediate a5 2- (4-Bromophenyl) -4,6-diphenyl-1,3,5-triazine (11.97 g, 34.8 mmol, 0.97 eq), Intermediate a4 (13.70 g, 35) .9 mmol), cesium carbonate (23.39 g, 71.8 mmol, 2.00 eq), and xylene (dehydrated grade, 206 mL, 15.0 v / w times) were placed in Schlenk tubes and replaced with argon. Palladium (II) acetate (0.806 g, 3.59 mmol, 0.10 eq) and tri-t-butylphosphonium tetrafluoroborate (3.12 g, 10.8 mmol, 0.30 eq) were added to this mixture under an argon stream. Was added, and the mixture was stirred at an outside temperature of 145 ° C. for 7 hours under a light-shielded airtight. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/9), it was confirmed that the raw materials were almost eliminated. The reaction solution was cooled to 50 ° C. or lower, the insoluble matter was filtered, and the insoluble matter was washed with toluene (100 mL, 7.3 v / w times amount). Subsequently, the organic layer in which the filtrate and the washing liquid were combined was washed with water (100 mL, 7.3 v / w times) and with saturated saline (100 mL, 7.3 v / w times). The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure on an evaporator. N-Hexane (100 mL, 7.3 v / w times) was added to the concentrated residue, dispersed and washed, and filtered. The obtained solid was dissolved in toluene (43 mL, 2.5 v / w times), and n-hexane (200 mL, 14.6 v / w times) was gradually added to precipitate crystals. The crystals were filtered and dried under reduced pressure at 75 ° C. to obtain a yellow solid of Intermediate a5 in a yield of 17.73 g and a yield of 71.7%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.01 (d, 2H), 8.82 (d, 4H), 7.65-7.54 (m, 8H), 7.48 (Dd, 1H), 7.29 (d, 1H), 6.99-6.92 (m, 2H), 6.81 (dd, 1H), 6.37 (d, 1H), 6.30 ( d, 1H), 3.64 (t, 2H), 2.62 (t, 2H), 1.83-1.79 (m, 2H), 1.71 (s, 6H), 0.90 (s) , 6H), 0.05 (s, 9H)

Mixing Intermediate a5 (8.90 g, 12.9 mmol), 1 mol / L hydrochloric acid (134 mL, 134 mmol, 10.4 eq) and tetrahydrofuran (134 ml, 15.1 v / w times) under synthetic shading of Intermediate A1. Then, the mixture was stirred at 20 to 30 ° C. for 19 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/14), it was confirmed that the raw materials were almost eliminated. A 11% aqueous potassium carbonate solution (150 g, 16.9 v / w times) is gradually added to this reaction solution while paying attention to foaming, and ethyl acetate (268 mL, 30.1 v / w times) is further added to separate the liquids. Then, the organic layer was washed with saturated brine (134 mL, 15.1 v / w times). The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure with an evaporator, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (233 g, 26.2 w / w times)). , Dichloromethane / n-hexane = 4/6 mixed solvent (evaporator) was flowed through the column, then the eluent was changed to ethyl acetate / n-hexane = 1/1 mixed solvent, and this was flowed through the column. By the above steps, a yellow solid of intermediate A1 was obtained in a yield of 6.72 g and a yield of 90.5%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.03 (d, 2H), 8.83 (d, 4H), 7.67-7.56 (m, 8H), 7.50 (Dd, 1H), 7.32 (d, 1H), 7.01-6.94 (m, 2H), 6.84 (dd, 1H), 6.39 (d, 1H), 6.33 ( d, 1H), 3.73-3.70 (m, 2H), 2.68 (t, 2H), 1.92-1.87 (m, 2H), 1.73 (s, 6H)

Under the synthetic shading of Intermediate a6, Intermediate A1 (5.00 g, 8.70 mmol) was dissolved in dichloromethane (125 mL, 25 v / w times) and cooled to an internal temperature of 5 ° C. or lower. Dess-Martin peryodinane (7.38 g, 17.4 mmol, 2.0 eq) was added to this solution, and the mixture was stirred at 5 ° C. or lower for 0.5 hours and further at 20 to 30 ° C. for 2.5 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/1), it was confirmed that the raw materials were almost eliminated. A saturated aqueous sodium hydrogen carbonate solution (125 mL, 25 v / w double volume) is added to this reaction solution to separate the liquid (first separate solution), and then dichloromethane (100 mL, 20 v / w double volume) is added to the upper layer to separate the liquid. The operation was repeated twice (second and third liquid separation). The lower layers obtained in the 1st to 3rd separations were combined and washed with saturated brine (100 mL, 20 v / w times). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure on an evaporator. The concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (75 g, 25 w / w times). In column chromatography, a mixed solvent (eluent) of dichloromethane / n-hexane = 4/6 was used as a column. The eluent was changed to a mixed solvent of dichloromethane / n-hexane = 6/4, and this was flowed through a column. By the above steps, a yield of 3.60 g of a yellow solid of intermediate a6 was obtained. It was obtained with a yield of 72.3%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.84 (s, 1H), 9.03 (d, 2H), 8.83-8.82 (m, 4H), 7.67 -7.55 (m, 8H), 7.49 (dd, 1H), 7.32 (d, 1H), 7.02-6.95 (m, 2H), 6.83 (dd, 1H), 6.38 (d, 1H), 6.33 (d, 1H), 2.94 (t, 2H), 2.78 (t, 2H), 1.73 (s, 6H)

Under the synthetic shading of intermediate A2, intermediate a6 (3.50 g, 6.11 mmol), t-butanol (123 mL, 35.1 v / w times), tetrahydrofuran (123 mL, 35.1 v / w times), Water (41 mL, 11.7 v / w times), 2-methyl-2-butene (13.52 g, 192.8 mmol, 31.6 eq), and potassium dihydrogen phosphate (5.82 g, 42.8 mmol, 7). 9.0 eq) was placed in a reaction vessel and stirring was started. Sodium chlorite (1.73 g, 15.9 mmol, 2.60 eq) was gradually added to this mixture, and the mixture was stirred at an internal temperature of 20 to 30 ° C. for 14 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane / acetic acid = 1/1/0.05), it was confirmed that the raw materials were almost eliminated. Ethyl acetate (123 mL, 35.1 v / w times) and water (123 mL, 35.1 v / w times) are added to this reaction solution to separate the layers, and the upper layer (organic layer) is saturated saline (123 mL, 35.1 v / w times). 35.1 v / w times) was washed. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure with an evaporator, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (140 g, 40 w / w times)). After flowing a mixed solvent (eluent) of dichloromethane / ethyl acetate = 3/7 on the column, the eluent was changed to a mixed solvent of dichloromethane / ethyl acetate = 5/5, and this was flowed on the column. 2. The solid obtained from the eluted fraction of the component was dissolved in tetrahydrofuran (100 mL, 28.6 v / w times), filtered, and then the filtrate was concentrated under reduced pressure with an evaporator to yield the yellow solid of intermediate A2. It was obtained in 35 g and a yield of 93.0%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.03 (d, 2H), 8.83-8.82 (m, 4H), 7.66-7.55 (m, 8H) , 7.49 (dd, 1H), 7.33 (d, 1H), 7.01-6.94 (m, 2H), 6.85 (dd, 1H), 6.38 (d, 1H), 6.32 (d, 1H), 2.94 (t, 2H), 2.68 (t, 2H), 1.72 (s, 6H)

(A-2) Synthesis of Monomers 1-MA, 1-EMA, 1-NEMA
Synthesis of monomer 1-MA

Triethylamine (0.478 g, 3.92 mmol, 4.50 eq) in a solution of intermediate A1 (0.50 g, 0.87 mmol) and dichloromethane (dehydrated grade, 10 mL, 20 v / w times) under a shaded argon atmosphere. ), 2,6-di-t-butyl-p-cresol (BHT) (0.001 g), and methacryloyl chloride (0.136 g, 1.31 mmol, 1.50 eq) are added in this order, and the internal temperature is 20 to 30 ° C. Was stirred for 19 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/2), it was confirmed that the raw materials were almost eliminated. After distilling by adding dichloromethane (8 mL, 16 v / w times) and water (20 mL, 40 v / w times) to this reaction solution, the organic layer is separated by a saturated aqueous sodium hydrogen carbonate solution (20 mL, 40 v / w times). ) Twice, washed once with water (20 mL, 40 v / w times), and further washed once with saturated brine (20 mL, 40 v / w times). The washed organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/4 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (65 g, 130 w / w times)). Chloroform (5 mL, × 10 v / w) is added to the solid obtained from the elution fraction of the target component to dissolve it, and this solution is gradually dissolved in a mixed solution of methanol / water = 4/1 (40 mL, 80 v / w times). It was dropped to precipitate a solid. The precipitated solid was separated by filtration, and chloroform (5 mL, 10 v / w times) was added to dissolve the solid, and this solution was gradually added dropwise to n-hexane (40 mL, 80 v / w times) to precipitate the solid. .. Further, the precipitated solid was filtered off, chloroform (5 mL, 10 v / w times) and BHT (0.001 g) were added, and the mixture was concentrated under reduced pressure with an evaporator to yield 0 yield of the yellow solid of monomer 1-MA. It was obtained at .48 g and a yield of 85.8%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.02 (d, 2H), 8.82 (d, 4H), 7.65-7.55 (m, 8H), 7.48 (D, 1H), 7.29 (d, 1H), 7.00-6.93 (m, 2H), 6.81 (dd, 1H), 6.38 (d, 1H), 6.31 ( d, 1H), 6.11 (s, 1H), 5.56 (s, 1H), 4.18 (t, 2H), 2.68 (t, 2H), 2.01-1.95 (m) , 5H), 1.72 (s, 6H)

Synthesis of Monomer 1-EMA

4-Dimethylaminopyridine (0.501 g, 3) in a solution of intermediate A2 (1.00 g, 1.70 mmol) and N, N-dimethylformaldehyde (10 mL, 10 v / w times) under a shaded argon atmosphere. .70 mmol, 2.00 eq), 2-hydroxyethyl methacrylate (0.243 g, 1.87 mmol, 1.10 eq), 2,6-di-t-butyl-p-cresol (BHT) (0.001 g), And 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.488 g, 2.55 mmol, 1.50 eq) were added, and the mixture was stirred at an internal temperature of 20 to 30 ° C. for 18 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/2), it was confirmed that the raw materials were almost eliminated. Ethyl acetate (30 mL, 30 v / w times) and water (15 mL, 15 v / w times) are added to this reaction solution to separate the layers, and the organic layer is separated with saturated brine (15 mL, 15 v / w times). Washed. The washed organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/3 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (135 g, 135 w / w times)). BHT (0.001 g) was added to the elution fraction of the target component. By the above steps, a yellow liquid of monomer 1-MA was obtained in a yield of 1.08 g and a yield of 90.7%.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.03 (d, 2H), 8.84-8.82 (m, 4H), 7.67-7.55 (m, 8H) , 7.49 (dd, 1H), 7.32 (d, 1H), 7.01-6.94 (m, 2H), 6.83 (dd, 1H), 6.38 (d, 1H), 6.31 (d, 1H), 6.11 (s, 1H), 5.57 (t, 1H), 4.35 (s, 4H), 2.93 (t, 2H), 2.65 (t) , 2H), 1.93 (s, 3H), 1.72 (s, 6H)

Synthesis of Monomer 1-NEMA

Dibutyltin dilaurate (0.199 g, 0.26 mmol) in a solution of intermediate A1 (0.50 g, 0.87 mmol) and tetrahydrofuran (dehydrated grade, 20 mL, 40 v / w times) under a shaded argon atmosphere 0.30 eq) and 2,6-di-t-butyl-p-cresol (BHT) (0.001 g) were added, and stirring was started. 2-Methacryloyloxyethyl isocyanate (0.474 g, 3.05 mmol, 3.50 eq) was gradually added to this mixture, and the mixture was stirred at an internal temperature of 20 to 30 ° C. for 2 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/1), it was confirmed that the raw materials were almost eliminated. Chloroform (20 mL, 40 v / w times) and water (20 mL, 40 v / w times) are added to this reaction solution to separate the solutions, and the organic layer is washed with saturated brine (20 mL, 40 v / w times). did. The washed organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/3 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (70 g, 140 w / w times)). Chromatography (5 mL, 10 v / w times) is added to the solid obtained from the elution fraction of the target component to dissolve it, and this solution is gradually added dropwise to n-hexane (40 mL, 80 v / w times) to precipitate the solid. The precipitated solid was filtered off, dissolved in chloroform under the same conditions as above, precipitated again in n-hexane, and the precipitated solid was filtered off. Chromatography (5 mL, 10 v) was added to the obtained solid. (/ W times) and BHT (0.001 g) were added and concentrated under reduced pressure with an evaporator to obtain a yellow solid of monomer 1-NEMA in a yield of 0.59 g and a yield of 92.9%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 9.02 (d, 2H), 8.83-8.81 (m, 4H), 7.66-7.55 (m, 8H) , 7.48 (dd, 1H), 7.29 (d, 1H), 7.00-6.93 (m, 2H), 6.81 (dd, 1H), 6.38 (d, 1H), 6.31 (d, 1H), 6.12 (s, 1H), 5.59 (t, 1H), 4.93 (s, 1H), 4.24-4.10 (m, 4H), 3 .51-3.45 (m, 2H), 2.64 (t, 2H), 1.94-1.91 (m, 5H), 1.72 (s, 6H)

[B] Monomer synthesis 2
As shown below, here, intermediate B1 was synthesized, and monomer 2-MA and monomer 2-NEMA (TADF-containing monomer) were synthesized from intermediate B1.

(B-1) Synthesis Step of Intermediate B1 Intermediate B1 was synthesized by the following synthesis route. In the following reaction formula, in the synthetic route, in the following reaction formula, TBS represents a t-butyldimethylsilyl group.

Magnesium (3.50 g, 144 mmol, 1.19 eq) and tetrahydrofuran (17.5 mL, 0.44 v / w times) were heated to an internal temperature of 75 ° C. under the synthetic nitrogen atmosphere of intermediate b1, and 1,2- Dibromoethane (0.20 g, 1.1 mmol, 0.01 eq) was added. A solution of intermediate a1 (40.0 g, 121 mmol) and tetrahydrofuran (320 mL, 8.0 v / w times) was gradually added dropwise to this mixture, followed by reaction for 3 hours. Gradually dip this reaction into a solution of 2,4-dichloro-6-phenyl-1,3,5-triazine (26.62 g, 121 mmol, 1.00 eq) in tetrahydrofuran (1100 mL, 2.75 v / w times). The mixture was added dropwise and reacted at an internal temperature of 55 ° C. for 22 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. A saturated aqueous solution of ammonium chloride and diisopropyl ether were added to this reaction solution to separate the layers, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure with an evaporator. The concentrated residue was purified by column chromatography (silica gel: Wakosil C-300) to obtain white crystals of intermediate b1 in a yield of 25.29 g and a yield of 50.4%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.48 (d, 2H), 7.62 (t, 1H), 7.51-7.43 (m, 3H), 7.25 -7.00 (m, 5H), 3.61 (m, 2H), 2.64 (m, 2H), 1.87-1.74 (m, 2H), 0.85 (s, 9H), 0.00 (s, 6H)

Synthesis of Intermediate b2 Intermediate b1 (5.00 g, 11.7 mmol), 4-bromophenylboronic acid (2.74 g, 13.6 mmol, 1.20 eq), tetrahydrofuran (100 mL, 20 v / w times), water. (50 mL, 10 v / w times) and potassium carbonate (9.40 g, 68.0 mmol, 5.80 eq) were placed in a reaction vessel and stirring was started. Tetrakis (triphenylphosphine) palladium (0) (0.263 g, 0.23 mmol, 0.02 eq) was added to this mixture, and the mixture was reacted under reflux for 21 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Water and diisopropyl ether were added to this reaction solution to separate the layers, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. The concentrated residue was purified by column chromatography (silica gel: Wakosil C-300) to obtain a colorless transparent liquid of intermediate b2 in a yield of 3.59 g and a yield of 56.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.66 (d, 2H), 8.57 (t, 4H), 7.62 (d, 2H), 7.54-7.47 (M, 3H), 7.21 (d, 2H), 3.60 (t, 2H), 2.73 (t, 2H), 1.80-1.86 (m, 2H), 0.91 ( s, 9H), 0.07 (s, 6H)

Synthesis of Intermediate b3 9-Benzyl-9H-carbazole (24.0 g, 93.3 mmol) and N-bromosuccinimide (340 g, 191 mmol, 2.05 eq) were added to chloroform and stirred at an internal temperature of 40 ° C. for 2 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Water was added to the reaction solution to separate the layers, the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. Methanol was added to the concentrated residue, and the mixture was stirred and then filtered and dried to obtain a white solid of intermediate b3 in a yield of 36.78 g and a yield of 95.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.16 (s, 2H), 7.52 (d, 2H), 7.28-7.20 (m, 5H), 7.07 -7.04 (m, 2H), 5.45 (s, 2H)
Synthesis of Intermediate b4 Under an argon atmosphere, Intermediate b3 (15.0 g, 36.1 mmol), toluene (deoxidized grade, 600 mL, 40 v / w times), bis (dibenzylideneacetone) palladium (0) (215 mg). , 0.23 mmol, 0.007 eq), tri-t-butylphosphonium tetrafluoroborate (252 mg, 0.87 mmol, 0.024 eq), sodium t-butoxide (12.1 g, 126 mmol, 3.5 eq), and diphenylamine. (13.8 g, 81.5 mmol, 2.26 eq) was placed in a reaction vessel, and the mixture was stirred at an internal temperature of 100 ° C. for 25 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Water was added to the reaction solution to separate the layers, the organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure with an evaporator, whereby a green solid of intermediate b4 was obtained almost quantitatively with a yield of 21.4 g.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 7.76 (s, 2H), 7.33-7.16 (m, 17H), 7.05 (d, 8H), 6.92 (T, 4H), 5.46 (s, 2H)

Synthesis of Intermediate b5 Intermediate b4 (22.0 g, 26.9 mmol) and potassium t-butoxide (10.4 g, 92.7 mmol, 3.4 eq), dimethyl sulfoxide (220 mL, 10 v / w times) and toluene (220 mL, 10 v / w times) was added, and the mixture was heated to an internal temperature of 50 ° C. while blowing air and stirred for 4 hours. Potassium t-butoxide (2.50 g, 22.3 mmol, 0.83 eq) was added to this mixture, and the mixture was stirred at an internal temperature of 20 to 30 ° C. for 16 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Water and diisopurpil ether were added to this reaction solution to separate the layers, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure with an evaporator. Chloroform was added to the concentrated residue, and the mixture was stirred and then filtered and dried to obtain intermediate b5. Further, the filtrate was concentrated under reduced pressure with an evaporator, and the concentration residue was purified by column chromatography (silica gel: Wakosil C-300) to recover the intermediate b5 remaining in the filtrate. Through the above steps, an ocher solid of Intermediate b5 was obtained in a total yield of 18.65 g and a yield of 96.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 7.50-6.50 (m, 27H)

Synthesis of Intermediate b6 Under a light-shielded argon atmosphere, Intermediate b2 (5.00 g, 8.92 mmol), toluene (deoxidized grade, 100 mL, 20 v / w times), bis (dibenzylideneacetone) palladium (0) (53.1 mg, 0.06 mmol, 0.007 eq), tri-t-butylphosphonium tetrafluoroborate (62.3 mg, 0.21 mmol, 0.024 eq), sodium t-butoxide (3.00 g, 31.2 mmol). , 3.5 eq), and intermediate b5 (4.50 g, 8.97 mmol, 1.01 eq) were placed in a reaction vessel and stirred at an internal temperature of 100 ° C. for 22 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Water, diisopropyl ether and dichloromethane were added to the reaction solution to separate the layers, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure with an evaporator. The concentrated residue was purified by column chromatography (silica gel: Wakosil C-300) to obtain a yellow solid of intermediate b6 in a yield of 6.82 g and a yield of 76.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.93 (d, 2H), 8.72 (d, 2H), 8.63 (d, 2H), 7.76-7.69 (M, 4H), 7.56-7.41 (m, 3H), 7.40 (d, 2H), 7.33 (d, 2H), 7.19-7.14 (m, 10H), 7.01 (d, 8H), 6.89 (t, 4H), 3.60 (t, 2H), 2.75 (t, 2H), 1.82-1.86 (m, 2H), 0 .85 (s, 9H), 0.00 (s, 6H)

Synthetic of Intermediate B1 Under shading, 1 mol / L hydrochloric acid (110 mL, 110 mmol, 16.4 eq) was added to a solution of intermediate b6 (6.70 g, 6.83 mmol) in tetrahydrofuran (220 mL, 33 v / w times). The mixture was heated to an internal temperature of 50 ° C. and stirred for 5 hours. When this reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Water and diisopropyl ether were added to this reaction solution to separate the layers, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. The concentrated residue was purified by column chromatography (silica gel: Wakosil C-300) to obtain a yellow solid of Intermediate B1 in a yield of 5.03 g and a yield of 85.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 9.00 (d, 2H), 8.80 (d, 2H), 8.73 (d, 2H), 7.85-7.75 (M, 4H), 7.65-7.55 (m, 3H), 7.48 (d, 2H), 7.43 (d, 2H), 7.28-7.20 (m, 10H), 7.09 (d, 8H), 6.93 (t, 4H), 3.74 (t, 2H), 2.86 (t, 2H), 2.03-1.99 (m, 2H)

(B-2) Synthesis step of monomers 2-MA and 2-NEMA
Synthesis of monomer 2-MA

Triethylamine (0.26 g, 2.13 mmol, 4.62 eq) in a solution of intermediate B1 (0.40 g, 0.46 mmol) and dichloromethane (dehydrated grade, 10 mL, 25 v / w times) under a light-shielded argon atmosphere. ), 2,6-di-t-butyl-p-cresol (BHT) (0.001 g), and methacryloyl chloride (0.074 g, 0.71 mmol, 1.54 eq) in this order, and the internal temperature is 20 to 30. The mixture was stirred at ° C. for 19 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/2), it was confirmed that the raw materials were almost eliminated. Dichloromethane (10 mL, 25 v / w times) and water (20 mL, 50 v / w times) were added to this reaction solution to separate the solutions. The organic layer was washed with saturated brine (20 mL, 50 v / w times), dried over anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/4 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (60 g, 150 w / w times)). Chromatography (9 mL, 22.5 v / w times) was added to the solid obtained from the elution fraction of the target component to dissolve it, and this solution was gradually added dropwise to methanol (30 mL, 75 v / w times) to precipitate the solid. Chromatography (9 mL, 22.5 v / w times) was added to the obtained solid to dissolve it, and this solution was gradually added dropwise to n-hexane (30 mL, 75 v / w times) to precipitate. The solid was separated by filtration. Chromatography (20 mL, 40 v / w times) and BHT (0.001 g) were added to this solid, and the mixture was concentrated under reduced pressure with an evaporator to obtain a yellow solid of monomer 2-MA. It was obtained almost quantitatively at 0.44 g.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.02 (d, 2H), 8.82 (d, 2H), 8.74 (d, 2H), 7.84-7.80 (M, 4H), 7.66-7.60 (m, 3H), 7.50 (d, 2H), 7.43 (d, 2H), 7.26-7.22 (m, 10H), 7.10 (d, 8H), 6.96 (t, 4H), 6.15 (s, 1H), 5.61-5.59 (m, 1H), 4.24 (t, 2H), 2 .88 (t, 2H), 2.14-2.10 (m, 2H), 1.99 (s, 3H)

Synthesis of Monomer 2-NEMA

Dibutyltin dilaurate (0.090 g, 0.) in a solution of intermediate B1 (0.40 g, 0.46 mmol) and tetrahydrofuran (dehydrated grade, 15 mL, 37.5 v / w times) under a shaded argon atmosphere. 12 mmol, 0.26 eq) and 2,6-di-t-butyl-p-cresol (BHT) (0.001 g) were added and stirring was started. 2-Methacryloyloxyethyl isocyanate (0.22 g, 1.41 mmol, 3.07 eq) was gradually added to this mixture, stirred at an internal temperature of 20 to 30 ° C. for 2 hours, and then heated to 60 to 65 ° C. 4 Stirred for hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/2), it was confirmed that the raw materials were almost eliminated. Chloroform (20 mL, 50 v / w times) and water (20 mL, 50 v / w times) were added to this reaction solution to separate the solutions. The organic layer was washed with saturated brine (20 mL, 50 v / w times), dried over anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/3 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (60 g, 150 w / w times)). Chromatography (7 mL, 17.5 v / w times) was added to the solid obtained from the elution fraction of the target component to dissolve it, and this solution was gradually added dropwise to methanol (40 mL, 100 v / w times) to precipitate the solid. Chromatography (7 mL, 17.5 v / w times) was added to the obtained solid to dissolve it, and this solution was gradually added dropwise to n-hexane (40 mL, 100 v / w times) to precipitate. The solid was separated by filtration. Subsequently, chloroform (40 mL, 100 v / w times) was added to the solid to dissolve it, and the insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure with an evaporator and then left as a residue. Chromatography (7 mL, 17.5 v / w times) was added and dissolved, and this solution was gradually added dropwise to n-hexane (40 mL, 100 v / w times), and the precipitated solid was filtered off. Chromatography (520 mL, 50 v / w times) and BHT (0.001 g, 0.001 w / w times) are added to the solid, and the mixture is concentrated under reduced pressure with an evaporator to yield 0 yield of the yellow solid of monomer 2-NEMA. It was obtained almost quantitatively at .50 g.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 9.02 (d, 2H), 8.82 (d, 2H), 8.74 (d, 2H), 7.84-7.80 (M, 4H), 7.66-7.60 (m, 3H), 7.49 (d, 2H), 7.43 (d, 2H), 7.27-7.22 (m, 10H), 7.10 (d, 8H), 6.96 (t, 4H), 6.15 (s, 1H), 5.61 (s, 1H), 4.27-4.16 (m, 4H), 3 .55-3.47 (m, 2H), 2.84 (t, 2H), 2.07-2.02 (m, 2H), 1.97 (s, 3H)

[C] Monomer synthesis 3
As shown below, here, intermediate C1 was synthesized, and monomer 3-EMA (TADF-containing monomer) was synthesized from the intermediate C1.
(C-1) Synthesis Step of Intermediate C1 Intermediate C1 was synthesized by the following synthesis route. In the following reaction formula, Me represents a methyl group and Et represents an ethyl group.

Synthesis of Intermediate c1 To methyl 3- (4-hydroxyphenyl) propionate (23.70 g, 131.5 mmol) and potassium carbonate (34.55 g, 250 mmol, 1.9 eq), N, N-dimethylformiamide ( 237 mL, 10 v / w times) and toluene (237 mL, 10 v / w times) were added, refluxed for 3 hours, and then toluene was distilled off. The mixture was cooled to 100 ° C., 4-bromo-2-fluorobenzonitrile (26.30 g, 131.5 mmol, 1.0 eq) was added and stirred at an internal temperature of 100-110 ° C. for 6 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. The reaction solution was cooled, and water (475 mL, 20 v / w times) and diisopropyl ether (475 mL, 20 v / w times) were added in this order to separate the solutions. The aqueous layer was extracted twice with diisopropyl ether (475 mL, 20 v / w times), the organic layers were combined into one, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure with an evaporator. did. Diisopropyl ether (92 mL, 2.0 v / w times) was added to the concentrated residue to dissolve it, and n-hexane (184 mL, 4.0 v / w times) was gradually added to precipitate a solid. The solid was separated by filtration and dried to obtain a white solid of intermediate c1 in a yield of 35.10 g and a yield of 74.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 7.49 (d, 1H), 7.32-7.24 (m, 3H), 7.05 (d, 2H), 6.95 (S, 1H), 3.69 (s, 3H), 2.96 (t, 2H), 2.66 (t, 2H)

Synthesis of Intermediate c2 8 mol / L sodium hydroxide in a mixture of intermediate c1 (35.10 g, 97.6 mmol), ethanol (211 mL, 6 v / w times) and water (211 mL, 6 v / w times) An aqueous solution (48.8 mL, 390.4 mmol, 4.0 eq) was added dropwise, and the mixture was stirred under reflux for 4 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: chloroform / methanol = 9/1), it was confirmed that the raw materials had disappeared. After cooling the reaction solution, concentrated hydrochloric acid (35.7 mL, 429 mmol) was gradually added dropwise to precipitate a solid, which was cooled to 15 ° C. or lower. The reaction solution in which the solid was precipitated was stirred for 1 hour, and then the solid was filtered off and dried to obtain white crystals of intermediate c2 in a yield of 24.50 g and a yield of 69.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 7.72 (d, 1H), 7.44 (dd, 1H), 7.36 (d, 2H), 7.10 (d, 2H) ), 6.97 (d, 1H), 2.85-2.78 (m, 2H), 2.57-2.27 (m, 2H)

Synthesis of Intermediate c3 Intermediate c2 (8.94 g, 24.5 mmol) was mixed with concentrated sulfuric acid (44.7 mL, 5 v / w times) and then reacted at an internal temperature of 70 to 80 ° C. for 4 hours. When this reaction solution was analyzed by thin layer chromatography (developing solvent: chloroform / methanol = 9/1), it was confirmed that the raw materials had disappeared. After cooling this reaction solution, the reaction solution was poured into ice water to solidify it. The precipitated crystals were separated by filtration, washed with water (88 mL, 10 v / w times), washed with methanol (88 mL, 10 v / w times) and dried, and the yield of white crystals of intermediate c3 was 7. It was obtained in 60 g and a yield of 89.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.09 (d, 1H), 8.00 (dd, 2H), 7.79 (dd, 1H), 7.65 (dd, 1H) ), 7.59 (d, 1H), 2.97 (t, 2H), 2.63 (t, 2H)

Synthesis of Intermediate c4 Intermediate c3 (15.90 g, 45.9 mmol) was suspended in ethanol (159 mL, 10 v / w times), one drop of concentrated sulfuric acid was added, and the mixture was stirred under reflux for 6 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. The reaction mixture was cooled to 70 ° C., and water (159 mL, 10 v / w times) was added to precipitate a solid. The precipitated crystals were filtered off and dried to obtain white crystals of intermediate c4 in a yield of 16.60 g and a yield of 96.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.18 (d, 1H), 8.14 (d, 2H), 7.69 (dd, 1H), 7.61 (dd, 1H) ), 7.49 (dd, 1H), 7.41 (d, 1H), 4.13 (q, 2H), 3.07 (t, 2H), 2.69 (t, 2H), 1.24 (T, 3H)

Synthesis of Intermediate c5 Under an argon atmosphere under light-shielded conditions, Intermediate c4 (2.63 g, 7.01 mmol), 9,3': 6', 9''-tercarbazole (3.49 g, 7.01 mmol, 1). 0.0 eq), potassium carbonate (1.94 g, 14.02 mmol, 2.0 eq), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (Xphos) (0.40 g, 0.84 mmol, 0.12 eq) and tris (dibenzylideneacetone) dipalladium (0) (0.51 g, 0.42 mmol, 0.06 eq) suspended in toluene (super-dehydrated grade, 70 mL, 26.6 v / w times) The mixture was allowed to stir at an internal temperature of 100 ° C. for 22 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. Chloroform (70 mL, 26.6 v / w times) was added to this reaction solution, and the mixture was filtered. To the obtained filtrate, a mixed solution of water (70 mL, 26.6 v / w times) and concentrated hydrochloric acid (3.5 mL, 7.01 mmol, 1.0 eq) was added and separated (first separation). Further, chloroform (70 mL, 26.6 v / w) was added to the aqueous layer to separate the liquids (second liquid separation). Then, the organic layer obtained in the first separation and the organic layer obtained in the second separation were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure with an evaporator. Subsequently, a mixed solvent of chloroform / diisopropyl ether = 30/1 to 20/1 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: (650 g, 100 w / w times amount)) to be intermediate. Yellow crystals of body c5 were obtained with a yield of 3.98 g and a yield of 72.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.68 (d, 1H), 8.30 (d, 2H), 8.25 (d, 1H), 8.16 (dd, 4H) ), 7.93 (d, 1H), 7.86-7.80 (m, 3H), 7.67 (dd, 3H), 7.51 (d, 1H), 7.41-7.38 ( m, 8H), 7.31-7.25 (m, 4H), 4.16 (q, 2H), 3.13 (t, 2H), 2.74 (t, 2H), 1.24 (t) ， 3H)

Synthetic of Intermediate C1 Under light-shielded light, intermediate c5 (6.00 g, 7.58 mmol) was dissolved in tetrahydrofuran (76 mL, 12.6 v / w times) and a 2 mol / L sodium hydroxide aqueous solution (7.6 mL) was dissolved. , 15.2 mmol, 2.0 eq), and then stirred under heating under reflux for 7 hours. When the reaction solution was analyzed by thin layer chromatography, it was confirmed that the raw materials were almost eliminated. 2 mol / L hydrochloric acid (8.1 mL, 16.2 mmol, 2.1 eq) was gradually added dropwise to this reaction solution, and water (76 mL, 12.6 v / w times) and chloroform (152 mL, 25.2 v / w) were added dropwise. (W times the amount) was added to separate the liquids. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. Subsequently, a mixed solvent of chloroform / methanol = 10/1 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: (480 g, 80 w / w times)) to obtain the yellow color of the intermediate C1. Crystals were obtained with a yield of 5.60 g and a yield of 97.0%.
^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ [ppm]: 8.67 (d, 1H), 8.29-8.25 (m, 3H), 8.14 (d, 4H), 7.90 (D, 1H), 7.84-7.77 (m, 3H), 7.67-7.63 (m, 3H), 7.50 (d, 1H), 7.40-7.38 (m) , 8H), 7.31-7.24 (m, 4H), 3.14 (t, 2H), 2.82 (t, 2H)

(C-2) Monomer 3-EMA Synthesis Step
Synthesis of Monomer 3-EMA

4-Dimethylaminopyridine (5.0 mL, 5.7 v / w times) in a solution of intermediate C1 (0.88 g, 1.15 mmol) and N, N-dimethylformaldehyde (5.0 mL, 5.7 v / w times) under a shaded argon atmosphere. 0.34 g, 2.31 mmol, 2.0 eq), 2-hydroxyethyl methacrylate (0.15 g, 1.15 mmol, 1.0 eq), 2,6-di-t-butyl-p-cresol (BHT) ( 0.001 g) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.33 g, 1.73 mmol, 1.50 eq) were added, and the mixture was stirred at an internal temperature of 20 to 30 ° C. for 18 hours. When the reaction solution was analyzed by thin layer chromatography (developing solvent: ethyl acetate / n-hexane = 1/2), it was confirmed that the raw materials were almost eliminated. Ethyl acetate (30 mL, 34 v / w times) and water (15 mL, 17 v / w times) were added to this reaction solution to separate the solutions. The organic layer was washed with saturated brine (20 mL, 23 v / w times), dried over anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator. Subsequently, a mixed solvent of ethyl acetate / n-hexane = 1/3 was used as an eluent, and the concentrated residue was purified by column chromatography (silica gel: Wakosil C-300 (135 g, 153 w / w times)). A mixed solution of ethyl acetate / n-hexane = 2/1 (60 mL, 68 v / w times) was added to the elution fraction of the target component, and the mixture was washed 5 times with water (30 mL, 34 v / w times). The organic layer was dried over anhydrous sodium sulfate, BHT (0.001 g) was added, and the mixture was concentrated under reduced pressure to obtain a yellow liquid of monomer 3-EMA in a yield of 0.95 g and a yield of 94.1%. ..
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ [ppm]: 8.70 (d, 1H), 8.32 (d, 2H), 8.26 (d, 1H), 8.18 (d, 4H) ), 7.95 (d, 1H), 7.87-7.83 (m, 3H), 7.70-7.67 (m, 3H), 7.52 (d, 1H), 7.42 ( d, 8H), 7.33-7.28 (m, 4H), 6.13 (d, 1H), 5.61-5.59 (m, 1H), 4.38-4.36 (m, 4H), 3.15 (t, 2H), 2.80 (t, 2H), 1.95 (s, 3H)

[D] Synthesis of Acrylic Polymer Monomer 1-MA, Monomer 1-EMA, Monomer 1-NEMA, Monomer 2-MA, or Monomer 2-NEMA (TADF-containing monomer) and Methyl methacrylate (TADF-free monomer) The polymer and each homopolymer of monomer 1-EMA and monomer 3-EMA were synthesized by the following synthetic route. In the reaction formula below, R represents a side chain containing a TADF structure. ..

(D-1) Copolymer synthesis step
Synthesis of Copolymer 1-MA-28 A solution of monomer 1-MA (0.480 g, 0.75 mmol) and toluene (11.3 mL), methyl methacrylate (0.142 g, 1.42 mmol), and azodiisobutyronitol. (8.3 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 18 hours under shading. The reaction solution was added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Dichloromethane (9 mL) was added to this solid to prepare a solution, which was gradually added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Dichloromethane (9 mL) was added to this solid to prepare a solution, which was gradually added dropwise to n-hexane (50 mL), and the precipitated solid was filtered off. Dichloromethane (40 mL) was added to the obtained solid to dissolve it, and the mixture was filtered to remove insoluble matter. The filtrate was concentrated under reduced pressure with an evaporator, and dichloromethane (9 mL) was added to the residue to prepare a solution, which was gradually added dropwise to n-hexane (40 mL) to filter off the precipitated solid. The obtained solid was dried under reduced pressure at 90 ° C. for 2 hours to obtain copolymer 1-MA-28 in a yield of 0.45 g. When the molecular weight of Copolymer 1-MA-28 was measured, Mw (weight average molecular weight) was 18,000 and Mn (number average molecular weight) was 9,000. The unit ratio of the polymer calculated by NMR measurement was l = 72 and m = 28.

Synthesis of Copolymer 1-EMA-05 Monomer 1-EMA (0.150 g, 0.214 mmol) and toluene (13.4 mL) solution, methyl methacrylate (0.450 g, 4.50 mmol), and azodiisobutyronitrile ( 8.5 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 19 hours under shading. The reaction solution was added dropwise to methanol (50 mL), and the supernatant solution was removed. Dichloromethane (7 mL) was added to this residue to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the precipitated solid was filtered off. Dichloromethane (30 mL) was added to this solid to dissolve it, and the mixture was filtered to remove insoluble matters, and then the filtrate was concentrated under reduced pressure with an evaporator to obtain a solid residue. Dichloromethane (7 mL) was added to this solid to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the operation of filtering the precipitated solid was repeated twice. Further, dichloromethane (5 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to n-hexane (50 mL), and the operation of filtering the precipitated solid was repeated twice, and then the solid was cooled at 80 ° C. By drying under reduced pressure for 2 hours, the desired copolymer 1-EMA-05 was obtained in a yield of 0.35 g. When the molecular weight of the copolymer 1-EMA-05 was measured, Mw (weight average molecular weight) was 18,000 and Mn (number average molecular weight) was 11,000. The unit ratio of the polymer calculated by NMR measurement was l = 95 and m = 5.

Synthesis of Copolymer 1-EMA-15 Monomer 1-EMA (0.297 g, 0.41 mmol) and toluene (10.0 mL) solution, methyl methacrylate (0.161 g, 1.61 mmol), and azodiisobutyronitrile ( 8.3 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 18 hours under shading. The reaction solution was added dropwise to methanol (50 mL), and the supernatant solution was removed. Dichloromethane (8 mL) was added to this residue to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the precipitated solid was filtered off. Dichloromethane (30 mL) was added to this solid to dissolve it, and the mixture was filtered to remove insoluble matters, and then the filtrate was concentrated under reduced pressure with an evaporator to obtain a solid residue. Dichloromethane (8 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the operation of filtering the precipitated solid was repeated twice. Further, dichloromethane (8 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to n-hexane (50 mL), and the operation of filtering the precipitated solid was repeated twice, and then the solid was cooled at 70 ° C. By drying under reduced pressure for 3 hours, the desired copolymer 1-EMA-15 was obtained in a yield of 0.20 g. When the molecular weight of the copolymer 1-EMA-15 was measured, Mw (weight average molecular weight) was 15,000 and Mn (number average molecular weight) was 8,000. The polymer unit ratio calculated by NMR measurement was l = 85 and m = 15 (from the calculation formula).

Synthesis of Copolymer 1-EMA-31 Monomer 1-EMA (0.350 g, 0.5 mmol) and toluene (10.0 mL) solution, methyl methacrylate (0.100 g, 1.00 mmol), and azodiisobutyronitrile ( 6.8 mg) was placed in a Schlenk tube. After replacing the inside of the container with argon, the container was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 18 hours under shading. The reaction solution was added dropwise to methanol (50 mL), and the supernatant solution was removed. Dichloromethane (8 mL) was added to this residue to dissolve it, and the mixture was gradually added dropwise to methanol (50 mL) to filter off the precipitated solid. Dichloromethane (30 mL) was added to this solid to dissolve it, and the mixture was filtered to remove insoluble matters, and then the filtrate was concentrated under reduced pressure with an evaporator to obtain a solid residue. Dichloromethane (8 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the operation of filtering the precipitated solid was repeated three times. Further, dichloromethane (8 mL) was added to the residue to make a solution, which was gradually added dropwise to n-hexane (50 mL), and the operation of filtering the precipitated solid was repeated twice, and then the solid was depressurized at 70 ° C. for 3 hours. By drying, the desired copolymer 1-EMA-31 (0.24 g) was obtained. When the molecular weight of the copolymer 1-EMA-31 was measured, Mw (weight average molecular weight) was 10,000 and Mn (number average molecular weight) was 7,000. The polymer unit ratio calculated by NMR measurement was l = 69 and m = 31.

Synthesis of Copolymer 1-EMA-51 Monomer 1-EMA (0.216 g, 0.31 mmol) and toluene (5.4 mL) solution, methyl methacrylate (0.025 g, 0.25 mmol), and azodiisobutyronitrile (. 3.0 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 16 hours under shading. The reaction solution was added dropwise to methanol (30 mL), and the supernatant solution was removed. Chloroform (10 mL) was added to this residue to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the precipitated solid was filtered off. Chloroform (30 mL) was added to this solid to dissolve it, and the mixture was filtered to remove insoluble matters, and then the filtrate was concentrated under reduced pressure with an evaporator to obtain a solid residue. Chloroform (10 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the precipitated solid was filtered off. Further, dichloromethane (8 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to n-hexane (50 mL), and the operation of filtering the precipitated solid was repeated twice, and then the solid was cooled at 90 ° C. By drying under reduced pressure for 2 hours, the desired copolymer 1-EMA-51 was obtained in a yield of 0.10 g. When the molecular weight of the copolymer 1-EMA-51 was measured, Mw (weight average molecular weight) was 8,000 and Mn (number average molecular weight) was 5,000. The polymer unit ratio calculated by NMR measurement was l = 49 and m = 51.

Synthesis of Copolymer 1-EMA-70 Monomer 1-EMA (0.432 g, 0.62 mmol) and toluene (10.0 mL) solution, methyl methacrylate (0.021 g, 0.21 mmol), and azodiisobutyronitrile ( 5.0 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 16 hours under shading. The reaction solution was added dropwise to methanol (50 mL), and the supernatant solution was removed. Tetrahydrofuran (10 mL) was added to this residue to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the precipitated solid was filtered off. Tetrahydrofuran (10 mL) is added to this solid to make a solution, which is gradually added dropwise to n-hexane (50 mL) to filter the precipitated solid, and then tetrahydrofuran (30 mL) is added to the solid to dissolve and filter. The insoluble matter was removed. The filtrate was concentrated under reduced pressure with an evaporator, and then tetrahydrofuran (10 mL) was added to the residue to prepare a solution, which was gradually added dropwise to n-hexane (50 mL) to filter off the precipitated solid. The obtained solid was dried under reduced pressure at 90 ° C. for 2 hours to obtain the desired copolymer 1-EMA-70 in a yield of 0.16 g. When the molecular weight of the copolymer 1-EMA-70 was measured, Mw (weight average molecular weight) was 7,000 and Mn (number average molecular weight) was 5,000. The unit ratio of the polymer calculated by NMR measurement was l = 30 and m = 70.

Synthesis of Copolymer 1-NEMA-29 A solution of monomer 1-NEMA (0.59 g, 0.81 mmol) and toluene (12.0 mL), methyl methacrylate (0.154 g, 1.54 mmol), and azodiisobutyronitrile ( 9.0 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 80 ° C. for 17 hours under shading. The reaction solution was added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Dichloromethane (9 mL) was added to this solid to prepare a solution, which was gradually added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Dichloromethane (9 mL) is added to this solid to make a solution, which is gradually added dropwise to n-hexane (50 mL) to filter the precipitated solid, and then dichloromethane (50 mL) is added to the solid to dissolve it, and the solid is filtered. The insoluble matter was removed. The filtrate was concentrated under reduced pressure with an evaporator, and dichloromethane (9 mL) was added to the residue to prepare a solution, which was gradually added dropwise to n-hexane (40 mL) to filter off the precipitated solid. The obtained solid was dried under reduced pressure at 90 ° C. for 2 hours to obtain the desired copolymer 1-NEMA-29 in a yield of 0.40 g. When the molecular weight of the copolymer 1-NEMA-29 was measured, Mw (weight average molecular weight) was 20,000 and Mn (number average molecular weight) was 9,000. The polymer unit ratio calculated by NMR measurement was l = 71 and m = 29.

Synthesis of Copolymer 2-MA-29 A solution of monomer 2-MA (0.220 g, 0.235 mmol) and toluene (4.8 mL), methyl methacrylate (0.045 g, 0.447 mmol), and azodiisobutyronitrile ( 2.6 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 75 ° C. for 18 hours under shading. The reaction solution was added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Chloroform (9 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to methanol (40 mL), and the operation of filtering the precipitated solid was repeated twice. Subsequently, chloroform (9 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to n-hexane (40 mL) to filter out the precipitated solid, and then chloroform (9 mL) was added to this solid. The solution was gradually added dropwise to a mixed solvent (40 mL) of n-hexane / chloroform = 3/1, and the operation of filtering the precipitated solid was repeated twice. Chloroform (40 mL) was added to the obtained solid to dissolve it, and the solid was filtered to remove insoluble matter. The filtrate was concentrated under reduced pressure with an evaporator, and then chloroform (9 mL) was added to the residue to prepare a solution, which was gradually added dropwise to n-hexane (40 mL) to filter off the precipitated solid. The solid was dried under reduced pressure at 90 ° C. for 2 hours to give the desired copolymer 2-MA-29 in a yield of 0.07 g. When the molecular weight of the copolymer 2-MA-29 was measured, Mw (weight average molecular weight) was 13,000 and Mn (number average molecular weight) was 10,000. The polymer unit ratio calculated by NMR measurement was l = 71 and m = 29.

Synthesis of Copolymer 2-NEMA-41 A solution of monomer 2-NEMA (0.25 g, 0.245 mmol) and toluene (5.3 mL), methyl methacrylate (0.044 g, 4.40 mmol), and azodiisobutyronitrile ( 2.7 mg) was placed in a Schlenk tube, the inside of the container was replaced with argon, the mixture was sealed, and the mixture was stirred at an outside temperature of about 75 ° C. for 18 hours under shading. The reaction solution was added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Chloroform (9 mL) was added to this solid to prepare a solution, which was gradually added dropwise to methanol (40 mL), and the precipitated solid was filtered off. Chloroform (9 mL) was added to this solid to prepare a solution, which was gradually added dropwise to n-hexane (40 mL), and the precipitated solid was filtered off. Further, chloroform (9 mL) was added to the obtained solid to dissolve it, and the mixture was gradually added dropwise to a mixed solvent (40 mL) of n-hexane / chloroform = 3/1 to filter out the precipitated solid, and then the solid was formed into a solid. Chloroform (40 mL) was added to dissolve, and the mixture was filtered to remove insoluble matter. After the filtrate is concentrated under reduced pressure with an evaporator, chloroform (9 mL) is added to the residue to make a solution, which is gradually added dropwise to a mixed solvent (40 mL) of n-hexane / chloroform = 3/1 to filter the precipitated solid. did. The obtained solid was dried under reduced pressure at 90 ° C. for 2 hours to obtain copolymer 2-NEMA-41 in a yield of 0.15 g. When the molecular weight of the copolymer 2-NEMA-41 was measured, Mw (weight average molecular weight) was 26,000 and Mn (number average molecular weight) was 17,000. The polymer unit ratio calculated by NMR measurement was l = 59 and m = 41.

(D-2) Synthetic step of homopolymer
Synthetic monomer 1-EMA (0.432 g, 0.62 mmol) of homopolymer 1-EMA-100, a solution of toluene (7.0 mL) and azodiisobutyronitrile (2.6 mg) are placed in a Schlenk tube, and the inside of the container is filled. After replacement with argon, the mixture was sealed, and stirred at an outside temperature of about 80 ° C. for 16 hours under shading. The reaction solution was added dropwise to methanol (50 mL), and the supernatant was removed to recover the solid residue. Dichloromethane (10 mL) was added to the solid to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the operation of filtering the precipitated solid was repeated twice. Subsequently, dichloromethane (10 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to n-hexane (50 mL) to filter the precipitated solid, and then dichloromethane (30 mL) was added to dissolve the solid. Insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure with an evaporator, and dichloromethane (10 mL) was added to the residue to prepare a solution, which was gradually added dropwise to n-hexane (50 mL) to filter off the precipitated solid. The obtained solid was dried under reduced pressure at 80 ° C. for 3 hours to obtain a homopolymer 1-EMA-100 in a yield of 0.13 g. When the molecular weight of the homopolymer 1-EMA-100 was measured, Mw (weight average molecular weight) was 7,000 and Mn (number average molecular weight) was 5,000.

Synthetic monomer of homopolymer 3-EMA-100 3-EMA (0.475 g, 0.54 mmol), a solution of toluene (7.6 mL) and azodiisobutyronitrile (2.3 mg) are placed in a Schlenk tube, and the inside of the container is filled. After replacement with argon, the mixture was sealed, and stirred at an outside temperature of about 80 ° C. for 17 hours under shading. The reaction solution was added dropwise to methanol (50 mL), and the supernatant was removed to recover the solid residue. Chloroform (10 mL) was added to the solid to prepare a solution, which was gradually added dropwise to methanol (50 mL), and the operation of filtering the precipitated solid was repeated twice. Subsequently, chloroform (10 mL) was added to the obtained solid to prepare a solution, which was gradually added dropwise to n-hexane (50 mL) to filter the precipitated solid, and then chloroform (45 mL) was added to dissolve the solid. Insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure with an evaporator, and then chloroform (10 mL) was added to the residue to prepare a solution, which was gradually added dropwise to n-hexane (50 mL) to filter off the precipitated solid. Subsequently, chloroform (10 mL) was added to the solid to prepare a solution, which was gradually added dropwise to a mixed solvent (50 mL) of n-hexane / acetone = 2/3, and the operation of filtering the precipitated solid was repeated twice. went. The obtained solid was dried under reduced pressure at 90 ° C. for 3 hours to obtain homopolymer 3-EMA-100 in a yield of 0.25 g. When the molecular weight of the homopolymer 3-EMA-100 was measured, Mw (weight average molecular weight) was 18,000 and Mn (number average molecular weight) was 10,000.

Table 1 summarizes the polymerization composition used for the synthesis of each polymer, the weight average molecular weight Mw of the obtained polymer, the number average molecular weight Mn, and the ratio (unit ratio) of the constituent units.

<Evaluation>
[1] Evaluation of Thermophysical Properties The powder of each synthesized acrylic polymer was placed in an aluminum pan and used as a measurement sample. Table 2 shows the results of measuring the glass transition temperature Tg for each of these samples by the differential scanning calorimetry method (manufactured by METTLER TOLEDO, DSC1). For comparison, the glass transition temperature Tg of DMAC-TRZ is also shown in Table 2.

As shown in Table 2, the glass transition temperature Tg was observed in both the acrylic polymer containing the TADF structure (DMAC-TRZ residue in this example) and the DMAC-TRZ, and it was confirmed that they had an amorphous structure. However, the glass transition temperature Tg of DMAC-TRZ was less than 100 ° C. On the other hand, the acrylic polymer had a glass transition temperature Tg higher than that of DMAC-TRZ by 25 ° C. or more, and most of them had a high glass transition temperature Tg of more than 120 ° C. From this, it was found that by introducing the TADF structure into the acrylic polymer, the thermal stability of the amorphous structure is remarkably improved as compared with the non-polymerized TADF.

[2] Evaluation of optical physical characteristics A thin film was prepared using the acrylic polymers shown in Table 3 among the synthesized acrylic polymers, and the optical physical characteristics were measured. The method for producing the thin film is as shown below. Each synthesized acrylic polymer is dissolved in chloroform to prepare a polymer solution, and this polymer solution is applied onto a quartz substrate at 1000 rpm by a spin coating method and dried to form a thin film composed of an acrylic polymer. did. For the prepared thin film, the emission quantum yield Φ _PL and the maximum emission wavelength λmax by the excitation light having the maximum intensity near 390 nm were measured. The results are shown in Table 3.

As shown in Table 3, the thin films of each acrylic polymer showed a _{high emission quantum yield Φ PL even though they were single films containing no host. Further, since a similarly high emission quantum yield Φ PL} was obtained even if the ratio of TADF-containing constituent units and the binding mode of TADF structure were changed, the unit ratio and the binding mode of TADF structure could be selected from a wide range, and the polymer It turned out that the degree of freedom in design is high.

(Example 2) Fabrication and evaluation of organic electroluminescence device Each thin film is formed on a glass substrate having an anode made of indium tin oxide (ITO) having a film thickness of 50 nm by a spin coating method or a vacuum vapor deposition method. Formed. Here, vacuum deposition was performed at a degree of vacuum of ^{10 -4 Pa or less.}
First, an aqueous solution of PEDOT: PSS was spin-coated on ITO at 4000 rpm and dried to form a thin film of PEDOT: PSS to a thickness of 40 nm. A chloroform solution of copolymer 1-EMA-15 was spin-coated on this at 1000 rpm and dried to form a thin film of copolymer 1-EMA-15 to a thickness of 70 nm.
Next, B4PyMPM was deposited to a thickness of 60 nm on the thin film of the copolymer 1-EMA-15 to form a thin film of B4PyMPM, and Liq was deposited on the thin film to a thickness of 1 nm to form Liq. A thin film was formed. Further, Al was vapor-deposited to a thickness of 80 nm to form a cathode to obtain an organic electroluminescence device (EL device 1).
Further, an organic electroluminescence device (EL devices 2 to 5) was produced in the same manner as the EL device 1 except that the acrylic polymer shown in Table 4 was used instead of the copolymer 1-EMA-15.
Table for each EL element manufactured, the maximum external quantum efficiency EQE _MAX, 100 nit in (candelas per square meter) external quantum efficiency EQE _{100 nit,} the external quantum efficiency EQE _{1,000 nit} at 1,000 nit, the results of measurement of the CIE chromaticity coordinates at 1,000 nit Shown in 4.

As shown in Table 4, by using an acrylic polymer containing a TADF structure as a light emitting material, it is possible to achieve an external quantum efficiency close to 15% at the maximum, and to achieve an external quantum efficiency exceeding 10% even at 100 nits. I was able to do it. Further, since the external quantum efficiency could be greatly improved only by controlling the ratio m of the TADF-containing structural unit, it was found that the polymer design according to the device configuration was simple.

The acrylic polymer of the present invention has high luminous efficiency and can be formed into a stable amorphous film by a coating method. Therefore, by using the acrylic polymer of the present invention in the light emitting layer of the organic light emitting device, it is possible to realize an inexpensive organic light emitting device having high luminous efficiency. Therefore, the present invention has high industrial applicability.

1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Cathode

Claims (14)

Acrylic polymer that emits delayed fluorescence. The acrylic polymer according to claim 1, which has a partial structure in a side chain containing an electron donor group and an electron acceptor group. The acrylic polymer according to claim 1 or 2, which comprises a structural unit represented by the following general formula (1).
[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, DF represents a group capable of emitting delayed fluorescence, and L represents a single bond or a divalent linking group. ] The acrylic polymer according to claim 3, wherein the DF of the general formula (1) is a group represented by the following general formula (1a) or the following general formula (1b).
General formula (1a)
A ¹ − D ¹ ― * ¹
General formula (1b)
D ^2- A ^2- * ²
[In the general formulas (1a) and (1b), D ¹ and D ² each independently represent a donor group, and A ¹ and A ² each independently represent an acceptor group. * ¹ and * ² represent the bonding position to L in the general formula (1). ] The acrylic polymer according to claim 3, wherein the DF of the general formula (1) is a group represented by any of the following formulas.
[In each equation, * represents the position of connection to L in the general equation (1). The hydrogen atom in the formula may be substituted with a substituent. ] The acrylic polymer according to any one of claims 3 to 5, which is a copolymer containing the structural unit represented by the general formula (1) and the structural unit represented by the following general formula (3).
[In the general formula (3), R ² represents a hydrogen atom or a methyl group, and R ³ represents a substituted or unsubstituted alkyl group. ] A luminescent material containing the acrylic polymer according to any one of claims 1 to 6. A film containing the acrylic polymer according to any one of claims 1 to 6. The film according to claim 8, which is a coating film of the acrylic polymer. The film according to claim 8 or 9, which is an amorphous film. The film according to any one of claims 8 to 10, wherein the glass transition temperature Tg is 115 ° C. or higher. An organic light emitting device containing the acrylic polymer according to any one of claims 1 to 6. The organic light emitting device according to claim 12, wherein the acrylic polymer is contained in a light emitting layer. The organic light emitting device according to claim 12 or 13, which is an organic electroluminescence device.