# US 11,999,819 B2 · Formulation containing a highly branched polymer, highly branched polymer and electro-optical device containing this highly branched polymer

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- Number: US 11,999,819 B2
- Document ID: US11999819B2
- Status: Granted
- Kind: B2
- Application number: 17/260,202
- Filed: 2019-07-08
- Published: 2021-09-09
- Granted: 2024-06-04
- Earliest claimed: 2018-07-11
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Beate Burkhart; Miriam Engel; Matthias Hengst; Holger Heil; Manuel Hamburger; Christoph Leonhard; Gaelle Bealle
- Web page: https://patentgrep.com/patent/US11999819B2

## CPC

- C08G 73/026: {Wholly aromatic polyamines}
- C08G 61/12: Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C09D 165/00: Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers
- H10K 71/135: {using ink-jet printing}
- H10K 85/111: {comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene}
- H10K 85/115: {Polyfluorene; Derivatives thereof}
- H10K 85/151: {Copolymers}
- C08G 2261/135: Cross-linked structures
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/148: Side-chains having aromatic units
- C08G 2261/312: Non-condensed aromatic systems, e.g. benzene
- C08G 2261/314: Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G 2261/3142: fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
- C08G 2261/3162: Arylamines
- C08G 2261/411: Suzuki reactions
- C08G 2261/512: Hole transport
- C08G 2261/76: crosslinking
- C08G 2261/95: Use in organic luminescent diodes
- H10K 50/15: Hole transporting layers
- H10K 71/15: characterised by the solvent used
- H10K 71/40: Thermal treatment, e.g. annealing in the presence of a solvent vapour
- Y02E 10/549: Organic PV cells
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to formulations comprising at least one hyper-branched polymer which contains 30 to 70 mol % of at least one hole-transporting recurring unit A, 5 to 30 mol % of least one branching recurring unit B, 5 to 30 mol % of at least one further recurring unit C and 5 to 40 mol % of least one end group E, where the recurring units A, B and C are different from one another, and at least one organic solvent, characterised in that the formulation has a viscosity of ≤25 mPas. The present invention furthermore relates to the corresponding hyperbranched polymers and to processes for the preparation thereof. The present invention additionally also relates to the use of the hyperbranched polymers according to the invention in electronic or opto-electronic devices, and to electronic or opto-electronic devices containing these polymers.

## Claims

### Claim 1

A formulation comprising
A) at least one highly branched polymer which contains
30 to 70 mol % of at least one hole-transporting recurring unit A selected from triarylamine units of the following formula (A)
where
Ar1 to Ar3 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;
R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C═C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S, or CONR1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;
R1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and the dashed lines represent bonds to adjacent structural units in the polymer,
wherein Ar3 is substituted by Ar4 in at least one, of the two ortho positions, where Ar4 is a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R,
5 to 30 mol % of at least one branching recurring unit B,
5 to 30 mol % of at least one further recurring unit C selected from 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9′-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives, 1,2-: 1,3- or 1,4-phenylene, 1,2-, 1,3- or 1,4-naphthylene, 2,2′-, 3,3′- or 4,4′-biphenylylene, 2,2″-, 3,3″-, or 4,4″-terphenylylene, 2,2′-, 3,3′- or 4,4′-bi-1, 1′-naphthylylene or 2,2′″-, 3,3′″-, or 4,4″′-quaterphenylylene derivatives, and
5 to 40 mol % of at least one end group E,
where the recurring units A, B and C are different from one another, wherein the highly branched polymer has a molecular weight Mw in the range from 25,000 to 500,000 g/mol, and
B) at least one organic solvent having a boiling point of at least 200° C.,
wherein the formulation has a viscosity of from 2 to 20 mPas.

### Claim 2 (depends on 1)

The formulation according to claim 1, wherein the formulation comprises an organic solvent.

### Claim 3 (depends on 1)

The formulation according to claim 1, wherein the formulation comprises a mixture of two or more organic solvents.

### Claim 4 (depends on 1)

The formulation according to claim 1, wherein the concentration of the highly branched polymer in the formulation is in the range from 5 to 50 g/l.

### Claim 5 (depends on 1)

The formulation according to claim 1, wherein the branching recurring units B are selected from the structural units of the formulae (B1) to (B5)
where
Ar1 to Ar5 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;
R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C═C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S, or CONR1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;
R1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
Y is C or Si, and
the dashed lines represent bonds to adjacent structural units in the polymer.

### Claim 6 (depends on 1)

The formulation according to claim 1, wherein the end groups E are selected from structural units of the formulae (E1) to (E13)
where
R is on each occurrence, identically or differently, HK D, F, Cl, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═OXR1)2, S(═O)R1, S(═O)2R1, OSO2R, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S or CONR1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;
R1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
X is CR2, NR, SiR2, O, S, C═O or P═O,
p is 0, 1, 2, 3, 4 or 5,
m is 0, 1, 2, 3 or 4,
n is 0, 1, 2 or 3, and
the dashed line represents the bond to an adjacent structural unit in the polymer.

### Claim 7 (depends on 6)

The formulation according to claim 6, wherein the end groups E contain at least one, crosslinkable group Q.

### Claim 8 (depends on 1)

The formulation according to claim 1, wherein the highly branched polymer additionally contains 1 to 35 mol % of at least one crosslinkable structural unit D.

### Claim 9 (depends on 8)

The formulation according to claim 8, wherein the structural units D are selected from the structural units of the formulae (D1) to (D7)
where
Ar1 or Ar4 are on each occurence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;
Q is a crosslinkable group;
R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C═C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S or CONR1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;
R1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
X is CR2, NR, SiR2, O, S, C═O or P═O,
w is 0, 1, 2, 3, 4, 5 or 6,
r is 0 or 1,
s and t are each 0 or 1, where the sum (s+t)=1 or 2; and
the dashed lines represent bonds to adjacent structural units in the polymer.

### Claim 10 (depends on 8)

The formulation according to claim 8, wherein the structural units D are selected from the structural units of the formulae (D8) to (D21)
wherein in formulae (D1) to (D7), Q is a crosslinkable group; R is on each occurrence, identically or differently, H, D, F, Ci, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, Si(R1)2, C═O, C═S, C═N1, P(═O)(R1), SO, SO2, NR1, O, S or CONR1 and where one or more H atoms may be replaced by B, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1 or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F, where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
p is 0, 1, 2, 3, 4 or 5,
m is 0, 1, 2, 3 or 4,
n is 0, 1, 2 or 3,
y is 0, 1 or 2, and
the dashed lines represent bonds to adjacent structural units in the polymer, but with the proviso that, in relation to a phenylene group, the sum (p+y) is ≤5, and with the proviso that at least one y in each structural unit is ≥1.

### Claim 11 (depends on 1)

The formulation according to claim 1, wherein units of formula (A) includes Mo2-Br, Mo2-Bo, Mo3-Br or Mo4-Br

### Claim 12 (depends on 1)

The formulation according to claim 1, wherein the at least one structural unit of the formula (A) is selected from the structural units of the following formulae (A3), (A4) and (A5):
where Ar1, Ar2, Ar4 and R can adopt the meanings indicated above in relation to formula A,
m=0, 1, 2, 3 or 4,
n=0, 1, 2 or 3, and
X=CR2, NR, SiR2, O, S, C═O or P═O.