Patent Application
20250127007
The present invention relates to a composition, preferably being of a photocurable composition, comprising at least one light emitting moiety, a layer, process for fabricating a composition, a color conversion device, an optical device containing at least one color conversion device, method for fabricating a color conversion device, use of a composition, a chemical compound and use of a chemical compound.
WO 2017/054898 A1 describes a composition comprising red emission type nanocrystals, wetting and dispersing agent, propylene glycol monomethyl ether acetate as a solvent, an acryl polymer mixture including an acrylic unit including an acid group and a silane modified acrylic unit.
WO 2019/002239 A1 discloses a composition comprising a semiconducting light emitting nanoparticles, a polymer and a (meth)acrylate such as 1.4. cyclohexanedimethanol-monoacrylate having high viscosity around 90 cp.
However, the inventors newly have found that there are still one or more of considerable problems for which improvement is desired, as listed below. improved homogeneous dispersion of light emitting moieties in the composition, improved homogeneous dispersion of scattering particles in the composition, preferably improved homogeneous dispersion of both light emitting particles and scattering particles, more preferably improved homogeneous dispersion of light emitting moieties and/or scattering particles without solvent; composition having lower viscosity suitable for inkjet printing, preferably a composition which can keep lower viscosity even if it is mixed with high loading of light emitting moieties and/or scattering particles, even more preferably without solvent; composition having lower vapor pressure for large area uniform printing; a new composition realizing no residue around ink jet printing nozzle during/after ink jet printing, improved QY and/or EQE of light emitting moieties in the composition, improved QY and/or EQE of light emitting moieties after printing; improved thermal stability; easy printing without clogging at a printing nozzle; easy handling of the composition, improved printing properties; simple fabrication process; improved absorbance of blue light; improved solidity of a later made from the composition after inkjet printing; realizing blue shift of the peak maximum wavelength of light from a cured composition film layer, improved PWL value of the film layer, reducing/preventing red shift of the peak maximum wavelength of light emitted from a cured composition film layer.
The inventors aimed to solve one or more of the above-mentioned problems.
The present inventors have surprisingly found that one or more of the above described technical problems can be solved by the features as defined in the claims.
Namely, it is found a novel composition, composition, preferably it is being of a photocurable composition, more preferably it is being a photocurable composition for ink-jetting, comprising at least;
In some embodiments, said chemical compound may be attached to a surface of the light emitting moiety.
In another aspect, the present invention relates to a composition comprising a polymer derived or derivable from one or more of the reactive monomers of the composition of the present invention and optionally one or more of scattering particles, preferably the film is obtained or obtainable by curing the composition.
In another aspect, the present invention relates to a process of fabricating the composition of the present invention comprising at least; essentially consisting of, or consisting of, the following step Y1;
Preferably said chemical compound is not a polymer.
In another aspect, the present invention relates to use of the composition of the present invention, in an electronic device, optical device, sensing device or in a biomedical device or for fabricating an electronic device, sensing device, optical device or a biomedical device.
In another aspect, the present invention relates to a layer containing a composition of the present invention.
In another aspect, the present invention relates to a layer containing at least, essentially consisting of or consisting of;
Preferably said chemical compound is not a polymer. Here the term “solid content” means the content of the composition without solvent.
In another aspect, the present invention relates to a process of fabricating the layer of the present invention, wherein the process comprises at least, essentially consisting of or consisting of the following steps;
In another aspect, the present invention relates to a layer obtained or obtainable from the process.
In another aspect, the present invention further relates to a color conversion device (100) comprising at least, essentially consisting of or consisting of, a pixel, preferably said pixel is a 1st pixel (411) and/or a 2nd pixel (412), partly or fully filled with the layer of the present invention, comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
In another aspect, the present invention further relates to use of the composition of the present invention for fabricating the layer of the present invention or the device (100) of the present invention.
In another aspect, the present invention relates to a method for fabricating a color conversion device (100) of the present invention containing at least, essentially consisting of or consisting of, the following steps, preferably in this sequence;
In another aspect, the present invention further relates to a color conversion device (100) obtainable or obtained from the method of the present invention.
In another aspect, the present invention also relates to use of the color conversion device (100) of the present invention in an optical device (300) containing at least one functional medium (320) configured to modulate a light or configured to emit light.
In another aspect, the present invention furthermore relates to an optical device (300) containing at least one functional medium (320) configured to modulate a light or configured to emit light, and the color conversion device (100) of the present invention.
In another aspect, the present invention furthermore relates to a chemical compound represented by following chemical formula (IA);
In another aspect, the present invention furthermore relates to use of the chemical compound of the present invention in a composition, preferably in a photosensitive composition.
Further advantages of the present invention will become evident from the following detailed description.
In the present specification, symbols, units, abbreviations, and terms have the following meanings unless otherwise specified.
In the present specification, unless otherwise specifically mentioned, the singular form includes the plural form and “one” or “that” means “at least one”. In the present specification, unless otherwise specifically mentioned, an element of a concept can be expressed by a plurality of species, and when the amount (for example, mass % or mol %) is described, it means sum of the plurality of species. “and/or” includes a combination of all elements and also includes single use of the element.
In the present specification, when a numerical range is indicated using “to” or “-”, it includes both endpoints and units thereof are common. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.
In the present specification, the hydrocarbon means one including carbon and hydrogen, and optionally including oxygen or nitrogen. The hydrocarbyl group means a monovalent or divalent or higher valent hydrocarbon. In the present specification, the aliphatic hydrocarbon means a linear, branched or cyclic aliphatic hydrocarbon, and the aliphatic hydrocarbon group means a monovalent or divalent or higher valent aliphatic hydrocarbon. The aromatic hydrocarbon means a hydrocarbon comprising an aromatic ring which may optionally not only comprise an aliphatic hydrocarbon group as a substituent but also be condensed with an alicycle. The aromatic hydrocarbon group means a monovalent or divalent or higher valent aromatic hydrocarbon. Further, the aromatic ring means a hydrocarbon comprising a conjugated unsaturated ring structure, and the alicycle means a hydrocarbon having a ring structure but comprising no conjugated unsaturated ring structure.
In the present specification, the alkyl means a group obtained by removing any one hydrogen from a linear or branched, saturated hydrocarbon and includes a linear alkyl and branched alkyl, and the cycloalkyl means a group obtained by removing one hydrogen from a saturated hydrocarbon comprising a cyclic structure and optionally includes a linear or branched alkyl in the cyclic structure as a side chain.
In the present specification, the aryl means a group obtained by removing any one hydrogen from an aromatic hydrocarbon. The alkylene means a group obtained by removing any two hydrogens from a linear or branched, saturated hydrocarbon. The arylene means a hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.
In the present specification, when polymer has a plural types of repeating units, these repeating units copolymerize. These copolymerization are any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of any of these.
According to the present invention, the term “(meth)acrylate polymer” means a methacrylate polymer, an acrylate polymer or a combination of methacrylate polymer and an acrylate polymer.
The term “emission” means the emission of electromagnetic waves by electron transitions in atoms and molecules.
In the present specification, Celsius is used as the temperature unit. For example, 20 degrees means 20 degrees Celsius.
According to the present invention, in one aspect, the composition comprises at least, essentially consisting of or consisting of;
Optical Density per milligram (OD/mg) is a parameter that is used to characterize absorbance properties of light emitting material. Preferably, for this patent application Optical Density per milligram (OD/mg) is a parameter that is used to characterize absorbance properties of inorganic content of a light emitting inorganic nanoparticle. and OD value is measured for a solution of a light emitting moiety at concentration equal to 1 mg of inorganic content per 1 ml of solution recorded for 1 cm optical path.
Estimate inorganic content in total solids of light emitting nanoparticle using thermogravimetric analyser (TGA).
Weigh a required volume of a stock solution of a light emitting moiety (e.g. 100 uL), record the value displayed on the balance in grams to 4 decimal places, dilute said solution of a light emitting moiety with the same solvent to a required final volume (e.g. 25 mL) using volumetric flask. Transfer the obtained solution to a standard 1 cm path length UV/Vis cuvette, record the absorbance value at certain wavelength (e.g. 450 nm). The absorbance of the sample shall be 0.3 or more or 1.0 or less. If the absorbance of the sample does not fall into this range, a volume of said stock solution of a light emitting moiety and said final volume used for OD/mg evaluation shall be adjusted. Use the recorded absorbance value, concentration of a stock solution of a light emitting moiety and a value of inorganic content in total solids of light emitting nanoparticle to calculate OD/mg as demonstrated in the following example:
Values of OD/mg specified in the working examples of this patent application are Optical Density values per milligram of inorganic content evaluated at 450 nm.
Preferable OD/mg values specified in this patent application are Optical Density values per milligram of inorganic content evaluated at 450 nm.
UV/Vis spectra recorded using spectrophotometer Shimadzu UV-1800.
It is believed that the chemical compound is preferable to control viscosity of the composition accordingly. More preferably it can prevent increasement of viscosity of the composition and/or keeping a good solubility of the light luminescent moieties in a long term storage in the composition.
In a preferable embodiment of the present invention, said chemical compound further comprises at least one group selected from one or more of members of the group consisting of phosphine group, phosphine oxide group, phosphate group, phosphonate group, thiol group, tertiary amine group, primary amine group, carboxyl group, hetero cyclic group, silane group, sulfonic acid, hydroxyl group, phosphonic acid, preferably said group is a phosphate group, a phosphonate group, thiol group, primary amine group, a carboxyl group or a combination of any of these, more preferably it is a carboxyl group. Preferably said chemical compound is not a polymer.
It is believed that a phosphonate group, thiol group, primary amine group, a carboxyl group or a combination of any of these are more preferable since it has better attaching ability to the outer most surface of the inorganic part of the light emitting moiety (such as the surface of the inorganic part of quantum materials).
More preferably, said chemical compound is represented by following chemical formula (IA);
It is believed that said chemical compound is very preferable to control viscosity/solubility of the composition accordingly. And it is very preferable to prevent increasement of viscosity of the composition and/or keeping a good dispersibility of the light luminescent moieties in a long term storage in the composition. It is believed that said chemical compound represented by chemical formula (IA) realizes improved dispersibility of the light emitting moieties at higher concentration in the composition, improved PWL value of the composition/cured film, improved brightness of value of the composition/cured film, improved EQE value of the composition/cured film, improved printability of the composition. Further, it is believed that the chemical compound has improved compatibility with the composition, especially with the reactive monomer, more preferably with the (meth)acrylate monomer(s) in the composition.
In a preferred embodiment of the present invention, said Rc is represented by following chemical formula:
In a preferred embodiment of the present invention, the ratio of the total weight of the chemical compound to the total weight of the light emitting moiety is in the range from 0.01 to 10, preferably it is in the range from 0.02 to 2, more preferably from 0.03 to 1; in case of said light emitting moiety is an inorganic light emitting material, the ratio of the weight of the chemical compound to the weight of the inorganic part of the inorganic light luminescent material is in the range from 0.01 to 20, preferably from 0.02 to 4, more preferably from 0.03 to 2.
It is believed that said ratio of the total weight of the chemical compound to the total weight of the light emitting moiety is very more preferable from the viewpoint to control viscosity/solubility of the composition accordingly. And it is furthermore preferable to prevent increasement of viscosity of the composition and/or keeping a good dispersibility of the light luminescent moieties in a long term storage in the composition. It is believed that the said ratio more preferably realizes improved dispersibility of the light emitting moieties at higher concentration in the composition, improved PWL value of the composition/cured film, improved brightness of value of the composition/cured film, improved EQE value of the composition/cured film, improved printability of the composition.
In some embodiments, the light emitting moiety may optionally contain at least one additional ligand from the view point of controlling the chemical properties/optical properties of the light emitting moiety, preferably said ligand is different from the chemical compound, preferably said ligand comprises at least one straight-chain or branched chain alkyl group having carbon atoms 1 to 45, straight-chain or branched chain alkenyl group having carbon atoms 1 to 45 or straight-chain or branched chain alkoxyl group having carbon atoms 1 to 45, more preferably said ligand contains a saturated straight-chain or branched chain alkyl group having carbon atoms 1 to 45 or straight-chain or branched chain alkenyl group having carbon atoms 1 to 45. More details of the chemical compound is described in pages 59 to 62 below.
It is believed that the lower viscosity is important to make a low viscosity composition suitable for inkjet printing. Therefore, a (meth)acrylate monomer having the viscosity value within the above-mentioned parameter ranges are especially suitable to make a composition for inkjet printing. By using these (meth)acrylate monomer in a composition, when it is mixed with another material such as semiconducting light emitting nanoparticles with high loading, the composition can still keep lower viscosity within the range suitable for inkjet printing.
In a preferred embodiment of the present invention, the boiling point (B.P.) of said reactive monomer is 80° C. or more, preferably it is in the range from 80° C. to 400° C., even more preferably from 85° C. to 375° C., further more preferably from 90° C. to 350° C. for large area uniform inkjet printing.
It is believed that said high boiling point is also important to make a composition having a lower vapor pressure preferably less than 0.001 mmHg for large area uniform printing, it is preferable to use a reactive monomer, preferably a (meth)acrylate monomer, more preferably a (meth)acrylate monomer of formula (I), (II) and/or (Ill) having the viscosity value of 25 cP or less at 25° C. and the boiling point at least 80° C. or more, preferably it is in the range from 85° C. to 350° C., more preferably from 100° C. to 350° C. to make a composition suitable for large area uniform inkjet printing even if it is mixed with high loading of another materials such as high loading of semiconducting light emitting nanoparticles.
Here, the term “(meth)acrylate” is a general term for an acrylate and a methacrylate. Therefore, according to the present invention, the term “(meth)acrylate monomer” means a methacrylate monomer and/or a acrylate monomer.
According to the present invention, said B.P can be estimate by the known method such as like described in Science of Petroleum, Vol. 11. p. 1281 (1398).
According to the present invention, any types of publicly available acrylates and/or methacrylates represented by chemical formula (I) or (II) can be used preferably.
Especially for the first aspect, any types of publicly available acrylates and/or methacrylates having the viscosity value of 25 cP or less at 25° C. represented by chemical formula (I), (II) and/or (Ill) can be used.
Thus, according to the present invention, the reactive monomer of the composition is preferably a (meth)acrylate monomer selected from a mono-(meth)acrylate monomer, a di-(meth)acrylate monomer or a tri-(meth)acrylate monomer more preferably it is represented by following chemical formula (II);
In a preferable embodiment, the composition further comprises a (meth)acrylate monomer represented by following chemical formula (I) and/or a (meth)acrylate monomer represented by following chemical formula (III);
In a preferred embodiment of the present invention, the (meth)acrylate monomer of chemical formula (II) is in the composition and the mixing ratio of the (meth)acrylate monomer of chemical formula (I) to the (meth)acrylate monomer of chemical formula (II) is in the range from 1:99 to 99:1 (formula (I):formula (II)), preferably from 5:95 to 50:50, more preferably from 10:90 to 40:60, even more preferably it is from 15:85 to 35:65, preferably at least a purified (meth)acrylate monomer represented by chemical formula (I), (II) is used in the composition, more preferably the (meth)acrylate monomer of chemical formula (I) and the (meth)acrylate monomer of chemical formula (II) are both obtained or obtainable by a purification method.
In a preferred embodiment, the boiling point (B.P.) of said (meth)acrylate monomer of chemical formula (I) and/or chemical formula (II) is 80° C. or more, preferably the (meth)acrylate monomers of chemical formula (I) and chemical formula (II) are both 80° C. or more, more preferably it is in the range from 80° C. to 400° C., even more preferably from 85° C. to 375° C., further more preferably from 90° C. to 350° C.
In a preferred embodiment of the present invention, the viscosity of the composition is 35 cP or less at 25° C., preferably in the range from 1 to 35 cP, more preferably from 2 to 30 cP, even more preferably from 2 to 25 cP.
According to the present invention, said viscosity can be measured by rheometer Kinexus Ultra+(Netzsch) at 25° C. https://www.netzsch-thermal-analysis.com/en/products-solutions/rheology/kinexus-ultra/
Furthermore preferably, said R3 of formula (I) and R4 of formula (I) are, each independently of each other, selected from the following groups.
Particularly preferably, said R3 and R4 of formula (I) are, at each occurrence, independently or differently selected from the following groups.
Furthermore preferably, said formula (I) is NDDA (nonanediol diacrylate; BP: 342° C.), HDDMA (hexanediol dimethacrylate; BP: 307), HDDA (hexanediol diacrylate; BP: 295° C.) or DPGDA (BP: 31400).
It is believed that the (meth)acrylate monomer represented by following chemical formula (II) shows much lower viscosity value than the viscosity of the (meth)acrylate monomer of formula (I). Thus, by using the (meth)acrylate monomer represented by chemical formula (II) in combination of the (meth)acrylate monomer of chemical formula (I), a composition having much lower viscosity desirable for smooth inkjet printing can be realized, preferably without decreasing External Quantum Efficiency (EQE) value.
It is believed that said combination can realize a low viscosity composition comprising high amount of another materials, such as high loading of semiconducting light emitting nanoparticles. Thus, it is especially suitable for an inkjet printing when the composition comprises another material.
In a preferable embodiment of the present invention, the boiling point (B.P.) of said (meth)acrylate monomer of chemical formula (II) is 80° C. or more, preferably the (meth)acrylate monomer of chemical formula (II) is in the range from 80° C. to 400° C., more preferably from 85° C. to 375° C., further more preferably from 90° C. to 350° C. for large area uniform inkjet printing.
In a further preferable embodiment of the present invention, the boiling point (B.P.) of said (meth)acrylate monomer of chemical formula (I) and/or the boiling point (B.P.) of said (meth)acrylate monomer of chemical formula (II) is 80° C. or more, preferably the (meth)acrylate monomers of chemical formula (I) and chemical formula (II) are both 80° C. or more, more preferably it is in the range from 80° C. to 400° C., even more preferably from 85° C. to 375° C., further more preferably from 90° C. to 350° C. for large area uniform inkjet printing.
Furthermore preferably, said R7 of formula (II) is, at each occurrence, independently or differently, selected from the following groups.
The furthermore preferably, said formula (II) is Lauryl methacrylate (LM, viscosity 6 cP, BP: 142° C.) or Lauryl acrylate (LA, viscosity: 4.0 cP, BP: 313.2° C.).
It is believed that the higher amount of the (meth)acrylate monomer of chemical formula (I) to the total amount of the (meth)acrylate monomer of chemical formula (II) leads improved EQE of the composition, and the mixing weight ratio of the (meth)acrylate monomer of chemical formula (II) to the total amount of the (meth)acrylate monomer of chemical formula (I) less than 50 wt. % is preferable from the view point of viscosity of the composition, better ink-jetting properties of the composition.
Preferably, (meth)acrylate monomers purified by using silica column are used.
It is believed that an impurity removal from the (meth)acrylate monomers by the silica column purification leads improved QY of the semiconducting light emitting nanoparticle in the composition.
It is believed that the (meth)acrylate monomer of chemical formula (III) is useful to improve hardness/solidity of a layer made from the composition after inkjet printing.
According to the present invention, a publicly known (meth)acrylate monomer represented by following chemical formula (III) can be used to improve hardness/solidity of the layer after inkjet printing and cross linking.
Very preferably, Trimethylolpropane Triacrylate (TMPTA) is used as the (meth)acrylate monomer of chemical formula (III).
In a preferable embodiment of the present invention, the amount of the (meth)acrylate monomer of chemical formula (III) based on the total amount of (meth)acrylate monomers in the composition is in the range from 0.001 wt. % to 25 wt. %, more preferably in the range from 0.1 wt. % to 15 wt. %, even more preferably from 1 wt. % to 10 wt. %, further more preferably from 3 to 7 wt %.
Preferably, there (meth)acrylate monomers are purified by using silica column, are used.
It is believed that an impurity removal from the (meth)acrylate monomers by the silica column purification leads improved QY of the semiconducting light emitting nanoparticle in the composition.
According to the present invention, preferably the composition is configured to show the EQE value 23% or more, preferably 24% or more and less than 50%.
According to the present invention, said EQE is measured by the following EQE measurement process at room temperature which is based on using an integrating sphere, equipped with a 450 nm excitation light source coupled in via an optical fiber, and a spectrometer (C9920, Hamamatsu photonics), and which consists of a first measurement using air as the reference to detect the incident photons of the excitation light and a second measurement with the sample or test cell placed in front of the integrating sphere in between the opening of the integrating sphere and the exit of the optical fiber to detect the photons incident from the excitation light source transmitted through the sample and the photos emitted from the sample or test cell, whereas for both cases photons exiting the integrating sphere are counted by the spectrometer and EQE and BL calculation is done with the following equations and the number of photons of the excitation light and emission light is calculated by integration over the following wavelength ranges;
EQE=Photons[Emission light]/Photons[Excitation light measured without sample in place];
BL=Photons[Excitation light measured with sample in place]/Photons [Excitation light measured without sample in place];
According to the present invention, in a preferred embodiment, the viscosity of the composition is 35 cP or less at 25° C., preferably in the range from 1 to 35 cP, more preferably from 2 to 35 cP, even more preferably from 2 to 30 cP.
In a preferred embodiment of the present invention, the composition comprises a solvent 10 wt % or less based on the total amount of the composition, more preferably it is 5 wt % or less, more preferably it is a solvent free composition, preferably the composition does not comprise any one of the following solvent selected from one or more members of the group consisting of ethylene glycol monoalkyl ethers, such as, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ethers, such as, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethylene glycol alkyl ether acetates, such as, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates, such as, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones, such as, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, such as, ethanol, propanol, butanol, hexanol, cyclo hexanol, ethylene glycol, triethylene glycol and glycerin; esters, such as, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate; and cyclic asters, such as, gamma-butyro-lactone; chlorinated hydrocarbons, such as chloroform, dichloromethane, chlorobenzene, trimethyl benzenes such as 1,3,5-trimethylbenzene, 1,2,4-trimethyl benzene, 1,2,3-trimethyl benzene, docecylbenzene, cyclohexylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 3-isopropylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl and dichlorobenzene, preferably said solvent is propylene glycol alkyl ether acetates, alkyl acetates, ethylene glycol monoalkyl ethers, propylene glycol, and propylene glycol monoalkyl ethers.
It is believed that the less than 10 wt % of solvent in the composition leads improved ink-jetting and it can avoid 2nd or more ink-jetting onto the same pixel after evaporation of the solvent.
According to the present invention, it is desirable not to add any solvent to realize large area inkjet printing with improved uniformity without causing any clogging at a nozzle and/or with good dispersity of semiconducting light emitting nanoparticles and/or with good dispersity of scattering particles.
According to the present invention, preferably the composition further comprises an another material selected from one or more members of the group consisting of;
In some embodiments of the present invention, preferably the composition of the present invention comprises
According to the present invention, the polymer configured so that said polymer enables to the scattering particles to disperse in the composition comprises at least a repeating unit A comprising a phosphine group, phosphine oxide group, phosphate group, phosphonate group, thiol group, tertiary amine group, primary amine group, carboxyl group, hetero cyclic group, silane group, sulfonic acid, hydroxyl group, phosphonic acid, or a combination of thereof, preferably the repeating unit A comprises a tertiary amine, hydroxyl group, carboxyl group, silane group, thiol group, primary amine group, phosphine oxide group, phosphonic acid, or a phosphate group.
In some embodiments of the present invention, the repeating unit A and the repeating unit B are a constitutional repeating unit.
Even more preferably, the repeating unit A comprises a tertiary amine represented by following chemical formula (VII),
—NR12R13R14 (VII)
Even more preferably, R12 is a straight or a branched alkyl group having 1 to 30 carbon atoms; R13 is a straight or a branched alkyl group having 1 to 30 carbon atoms; R12 and R13 can be same or different of each other.
Furthermore preferably, R12 is methyl group, ethyl group, n-propyl group, or n-butyl group; R13 is methyl group, ethyl group, n-propyl group, or n-butyl group.
According to the present invention, in a preferred embodiment, the repeating unit A does not contain a salt.
In a preferred embodiment of the present invention, the polymer is a copolymer selected from the group consisting of graft copolymers, block copolymers, alternating copolymers, and random copolymers, preferably said copolymer comprises the repeating unit A, and repeating unit B that does not include any phosphine group, phosphine oxide group, phosphate group, phosphonate group, thiol group, tertiary amine, carboxyl group, hetero cyclic group, silane group, sulfonic acid, hydroxyl group, phosphonic acid, and a combination of thereof, more preferably the copolymer is a block copolymer represented by following chemical formula (VIII) or (IX),
An-Bm— (VIII)
Bo-An-Bm— (IX)
In a preferred embodiment of the present invention, the polymer chain of the repeating unit B is a polyethylene glycol.
More preferably, the repeating unit B comprises a chemical structure represented by following chemical formula (X),
Even more preferably, R15 can be a hydrogen atom, or methyl group, R16 can be an ethyl group, and n is an integer 1 to 5.
In some embodiments of the present invention, the surface of the core, or the outermost surface of one or more shell layers of the semiconducting light emitting nanoparticle can be partly or fully over coated by the polymer.
By using ligand exchange method, described in for example, Thomas Nann, Chem. Commun., 2005, 1735-1736, DOI: 10.1039/b-414807j, the polymer can be introduced onto the surface of the core or the outermost surface of the core of the semiconducting light emitting nanoparticle.
According to the present invention, in some embodiments, the content of said polymer is in the range from 1% to 500% by weight, more preferably in the range from 20% to 350% by weight, even more preferably from 50% to 200% by weight with respect to the total weight of the scattering particles.
In a preferred embodiment of the present invention, the weight average molecular weight (Mw) of the polymer is in the range from 200 g/mol to 30,000 g/mol, preferably from 250 g/mol to 5,000 g/mol, more preferably from 300 g/mol to 2,000 g/mol.
The molecular weight Mw is determined by means of GPC (=gel permeation chromatography) against an internal polystyrene standard.
As the polymer, commercially available wetting and dispersing additives which can be solved in non-polar and/or low polar organic solvent can be used preferably. Such as BYK-111, BYK-LPN6919, BYK-103, BYK-P104, BYK-163 ([trademark], from BYK com.), TERPLUS MD1000 series, such as MD1000, MD1100 ([trademark], from Otsuka Chemical), Poly(ethylene glycol) methyl ether amine (Sigma-Ald 767565 [trademark], from Sigma Aldrich), Polyester bis-MPA dendron, 32 hydroxyl, 1 thiol, (Sigma-Aid 767115 [trademark], from Sigma Aldrich), LIPONOL DA-T/25 (From Lion Specialty Chemicals Co.), Carboxymethyl cellulose (from Polyscience etc.), another wetting and dispersing additives disclosed in for examples, “Marc Thiry et. al., ACSNANO, American Chemical society, Vol. 5, No. 6, pp 4965-4973, 2011”, “Kimihiro Susumu, et. al., J. Am. Chem. Soc. 2011, 133, pp 9480-9496”.
Thus, in some embodiments of the present invention, the composition comprises at least the (meth)acrylate monomer of chemical formula (I), the (meth)acrylate monomer of chemical formula (II) and the polymer configured so that said polymer enables to the scattering particles to disperse in the composition, wherein the mixing ratio of the (meth)acrylate monomer of chemical formula (I):the (meth)acrylate monomer of chemical formula (II):the polymer is 1:5:0.01: to 5:4:1.
In some embodiments of the present invention, the composition comprises at least the (meth)acrylate monomer of chemical formula (III), the (meth)acrylate monomer of chemical formula (II) and the polymer configured so that said polymer enables to the scattering particles to disperse in the composition, wherein the mixing ratio of the (meth)acrylate monomer of chemical formula (III):the (meth)acrylate monomer of chemical formula (II):the polymer is 1:5:0.01 to 5:4:1 In some embodiment of the present invention, a composition comprises, essentially consisting of or consisting of, at least a polymer derived or derivable from the (meth)acrylate monomers of the composition of the present invention.
In a preferred embodiment of the present invention, said polymer is derived or derivable from all the (meth)acrylate monomers in the composition, for example, at least the (meth)acrylate monomer of chemical formula (I) and/or the (meth)acrylate monomer of chemical formula (II).
According to the present invention, as the scattering particles, publicly known small particles of inorganic oxides such as SiO2, SnO2, CuO, CoO, Al2O3TiO2, Fe2O3, Y2O3, ZnO, ZnS, MgO; organic particles such as polymerized polystyrene, polymerized PMMA; inorganic hollow oxides such as hollow silica or a combination of any of these, can be used. The amount of the scattering particles is preferably 30 wt % or less based on the total amount of the contents of the layer, preferably it is in the range from 25 to 0 wt %, more preferably it is in the range from 20 to 0 wt %, more preferably from 10 to 1 wt %.
In some embodiments of the present invention, the composition comprises iii) at least one semiconducting light emitting nanoparticle comprising a 1st semiconducting nanoparticle, optionally one or more shell layers covering at least a part of the 1st semiconducting nanoparticle, preferably the composition has EQE value 23% or more, preferably 24% or more and less than 50%.
According to the present invention, as a transparent polymer, a wide variety of publicly known transparent polymers suitable for optical devices, described in for example, WO 2016/134820A can be used preferably.
According to the present invention, the term “transparent” means at least around 60% of incident light transmit at the thickness used in an optical medium and at a wavelength or a range of wavelength used during operation of an optical medium. Preferably, it is over 70%, more preferably, over 75%, the most preferably, it is over 80%.
According to the present invention the term “polymer” means a material having a repeating unit and having the weight average molecular weight (Mw) 1000 g/mol, or more.
The molecular weight Mw is determined by means of GPC (=gel permeation chromatography) against an internal polystyrene standard.
In some embodiments of the present invention, the glass transition temperature (Tg) of the transparent polymer is 70° C. or more and 250° C. or less.
Tg is measured based on changes in the heat capacity observed in Differential scanning colorimetry like described in Rickey J Seyler, Assignment of the Glass Transition, ASTM publication code number (PCN) 04-012490-50.
For example, as the transparent polymer for the transparent matrix material, poly(meth)acrylates, epoxys, polyurethanes, polysiloxanes, can be used preferably.
In a preferred embodiment of the present invention, the weight average molecular weight (Mw) of the polymer as the transparent matrix material is in the range from 1,000 to 300,000 g/mol, more preferably it is from 10,000 to 250,000 g/mol.
According to the present invention, publicly known anti-oxidants, radical quenchers, photo initiators and/or surfactants can be used preferably like described in WO 2016/134820A.
In a preferable embodiment of the present invention, said light emitting moiety (110) is an organic and/or inorganic light emitting material, preferably it is an organic dye, inorganic phosphor and/or a semiconducting light emitting nanoparticle such as a quantum material.
In some embodiments of the present invention, the total amount of the light emitting moiety (110) is in the range from 0.1 wt. % to 90 wt. % based on the total amount of a pixel, preferably said pixel is a 1st pixel (161) and/or a 2nd pixel (162), preferably from 10 wt. % to 70 wt. %, more preferably from 20 wt. % to 60 wt. %. Preferably, said light emitting moiety is configured to emit light having peak maximum light wavelength in the range from 400 to 900, more preferably from 500 to 850 nm, even more preferably from 510 to 820 nm.
In a preferred embodiment of the present invention, in case of the light emitting moiety is an inorganic light emitting material, the average diameter of the inorganic part of the light emitting moiety is in the range from 1 nm to 18 nm, preferably it is from 2 to 15 nm, more preferably it is from 3 to 12 nm.
Thus, in some embodiments of the present invention, said light emitting moiety is an organic light emitting moiety and/or inorganic light emitting moiety, preferably it is an inorganic light emitting moiety, more preferably it is an inorganic light emitting moiety is an inorganic phosphor or a quantum material, preferably said light emitting moiety contains a ligand attached onto the outer most surface of the light emitting moiety, more preferably said ligand is the chemical compound of the present invention and/or it is at least one straight-chain or branched chain alkyl group having carbon atoms 1 to 45, straight-chain or branched chain alkenyl group having carbon atoms 1 to 45 or straight-chain or branched chain alkoxyl group having carbon atoms 1 to 45.
iii) Semiconducting Light Emitting Nanoparticle
According to the present invention, the term “semiconductor” means a material that has electrical conductivity to a degree between that of a conductor (such as copper) and that of an insulator (such as glass) at room temperature. Preferably, a semiconductor is a material whose electrical conductivity increases with the temperature.
The term “nanosized” means the size in between 0.1 nm to 150 nm, more preferably 3 nm to 50 nm.
Thus, according to the present invention, “semiconducting light emitting nanoparticle” is taken to mean that the light emitting material which size is in between 0.1 nm to 150 nm, more preferably 3 nm to 50 nm, having electrical conductivity to a degree between that of a conductor (such as copper) and that of an insulator (such as glass) at room temperature, preferably, a semiconductor is a material whose electrical conductivity increases with the temperature, and the size is in between 0.1 nm and 150 nm, preferably 0.5 nm to 150 nm, more preferably 1 nm to 50 nm.
According to the present invention, the term “size” means the average diameter of circle with an area equal to an average area of dark contrast features in TEM image.
The average diameter of the semiconducting nanosized light emitting particles is calculated based on 100 semiconducting light emitting nanoparticles in a TEM image created by a Tecnai G2 Spirit Twin T-12 Transmission Electron Microscope.
In a preferred embodiment of the present invention, the semiconducting light emitting nanoparticle of the present invention is a quantum sized material.
According to the present invention, the term “quantum sized” means the size of the semiconducting material itself without ligands or another surface modification, which can show the quantum confinement effect, like described in, for example, ISBN: 978-3-662-44822-9.
For example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, HgS, HgSe, HgSe, HgTe, InAs, InP, InPZn, InPZnS, InPZnSe, InPZnSeS, InPZnGa, InPGaS, InPGaSe, InPGaSeS, InPZnGaSeS and InPGa, InCdP, InPCdS, InPCdSe, InSb, AlAs, AlP, AlSb, Cu2S, Cu2Se, CuInS2, CuInSe2, Cu2(ZnSn)S4, Cu2(InGa)S4, TiO2 alloys and a combination of any of these can be used.
In a preferred embodiment of the present invention, the 1st semiconducting material comprises at least one element of the group 13 of the periodic table, and one element of the group 15 of the periodic table, preferably the element of the group 13 is In, and the element of the group 15 is P, more preferably the 1st semiconducting material is selected from the group consisting of InP, InPZn, InPZnS, InPZnSe, InPZnSeS, InPZnGa, InPGaS, InPGaSe, InPGaSeS, InPZnGaSeS and InPGa.
According to the present invention, a type of shape of the core of the semiconducting light emitting nanoparticle, and shape of the semiconducting light emitting nanoparticle to be synthesized are not particularly limited.
For examples, spherical shaped, elongated shaped, star shaped, polyhedron shaped, pyramidal shaped, tetrapod shaped, tetrahedron shaped, platelet shaped, cone shaped, and irregular shaped core and—or a semiconducting light emitting nanoparticle can be synthesized.
In some embodiments of the present invention, the average diameter of the core is in the range from 1.5 nm to 3.5 nm.
The average diameter of the core is calculated based on 100 semiconducting light emitting nanoparticles in a TEM image created by a Tecnai G2 Spirit Twin T-12 Transmission Electron Microscope by measuring the longest axis of each single particles.
In some embodiments of the present invention, at least one shell layer comprises or a consisting of a 1st element of group 12 of the periodic table and a 2nd element of group 16 of the periodic table, preferably, the 1st element is Zn, and the 2nd element is S, Se, or Te; preferably a first shell layer covering directly onto said core comprises or a consisting of a 1st element of group 12 of the periodic table and a 2nd element of group 16 of the periodic table, preferably, the 1st element is Zn, and the 2nd element is S, Se, or Te.
In a preferred embodiment of the present invention, at least one shell layer (a first shell layer) is represented by following formula (XI), preferably the shell layer directly covering the core is represented by the chemical formula (XI);
ZnSxSeyTez (XI)
In some embodiments of the present invention, said shell layer is an alloyed shell layer or a graded shell layer, preferably said graded shell layer is ZnSxSey, ZnSeyTez, or ZnSxTez, more preferably it is ZnSxSey.
In some embodiments of the present invention, the semiconducting light emitting nanoparticle further comprises 2nd shell layer onto said shell layer, preferably the 2nd shell layer comprises or a consisting of a 3rd element of group 12 of the periodic table and a 4th element of group 16 of the periodic table, more preferably the 3rd element is Zn, and the 4th element is S, Se, or Te with the proviso that the 4th element and the 2nd element are not same.
In a preferred embodiment of the present invention, the 2nd shell layer is represented by following formula (XI′),
ZnSxSeyTez (XI′)
In some embodiments of the present invention, said 2nd shell layer can be an alloyed shell layer.
In some embodiments of the present invention, the semiconducting light emitting nanoparticle can further comprise one or more additional shell layers onto the 2nd shell layer as a multishell.
According to the present invention, the term “multishell” stands for the stacked shell layers consisting of three or more shell layers.
For example, CdSe/CdS, CdSeS/CdZnS, CdSeS/CdS/ZnS, ZnSe/CdS, CdSe/ZnS, InP/ZnS, InP/ZnSe, InP/ZnSe/ZnS, InZnP/ZnS, InZnP/ZnSe, InZnP/ZnSe/ZnS, InGaP/ZnS, InGaP/ZnSe, InGaP/ZnSe/ZnS, InZnPS/ZnS, InZnPS ZnSe, InZnPS/ZnSe/ZnS, ZnSe/CdS, ZnSe/ZnS or combination of any of these, can be used. Preferably, InP/ZnS, InP/ZnSe, InP/ZnSe/ZnS, InZnP/ZnS, InZnP/ZnSe, InZnP/ZnSe/ZnS, InGaP/ZnS, InGaP/ZnSe, InGaP/ZnSe/ZnS.
Such semiconducting light emitting nanoparticles are publicly available (for example from Sigma Aldrich) and/or can be synthesized with the method described for example in U.S. Pat. Nos. 7,588,828 B, 8,679,543 B and Chem. Mater. 2015, 27, pp 4893-4898.
In some embodiments of the present invention, the composition comprises two or more semiconducting light emitting nanoparticles.
In some embodiments of the present invention, the composition comprises a plurality of semiconducting light emitting nanoparticles.
In some embodiments of the present invention, the total amount of the semiconducting light emitting nanoparticles is in the range from 0.1 wt. % to 90 wt. % based on the total amount of the composition, preferably from 10 wt. % to 70 wt. %, more preferably from 15 wt. % to 60 wt. %.
In some embodiments of the present invention, optionally, the light emitting moiety can be directly over coated by one or more ligands, or the outer most surface of the inorganic part of the semiconducting light emitting nanoparticle can be directly coated by the ligands. As an option, ligand coated semiconducting light emitting nanoparticle can be overcoated by a polymer forming a polymer beads having said semiconducting light emitting nanoparticle(s) inside.
As the ligands, phosphines and phosphine oxides such as Trioctylphosphine oxide (TOPO), Trioctylphosphine (TOP), and Tributylphosphine (TBP); phosphonic acids such as Dodecylphosphonic acid (DDPA), Tridecylphosphonic acid (TDPA), Octadecylphosphonic acid (ODPA), and Hexylphosphonic acid (HPA); amines such as Oleylamine, Dodecyl amine (DDA), Tetradecyl amine (TDA), Hexadecyl amine (HDA), and Octadecyl amine (ODA), Oleylamine (OLA), 1-Octadecene (ODE), thiols such as hexadecane thiol, dodecane thiol and hexane thiol; mercapto carboxylic acids such as mercapto propionic acid and mercaptoundecanoicacid; carboxylic acids such as oleic acid, stearic acid, myristic acid; acetic acid, Polyethylenimine (PEI), monofunctional polyethylene glycol PEG thiol (mPEG-thiol) or a derivatives of mPEG thiol, PEG carboxylate and a combination of any of these can be used.
Examples of such ligands have been described in, for example, the laid-open international patent application No. WO 2012/059931A.
In another aspect, the present invention relates to use of the composition of the present invention, in an electronic device, optical device, sensing device or in a biomedical device or for fabricating an electronic device, sensing device, optical device or a biomedical device.
In another aspect, the present invention relates to a layer containing the composition of the present invention.
In another aspect, the present invention relates to a layer containing at least, essentially consisting of or consisting of;
In a preferable embodiment, the layer thickness of the layer is in the range from 1 to 50 μm, preferably from 5 to 30, more preferably from 8 to 20, further more preferably from 10 to 15 um.
In another aspect, the present invention relates to a process of fabricating the layer of the present invention, wherein the process comprises at least, essentially consisting of or consisting of the following steps;
In another aspect, the present invention relates to a layer obtained or obtainable from the process.
A color conversion device (100) comprising at least a pixel, preferably said pixel is a 1st pixel (161) or a 2nd pixel (162), partly or fully filled with the layer of the present invention comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
According to the present invention, said pixel comprises at least a matrix material (120) containing a light emitting moiety (110) preferably said pixel is a 1st pixel (161) or a 2nd pixel (162). In a preferable embodiment, the pixel is a solid layer obtained or obtainable by curing the composition of the present invention containing at least one acrylate monomer together with at least one light emitting moiety (110), preferably said curing is a photo curing by photo irradiation, thermal curing or a combination of a photo curing and a thermal curing.
In some embodiments of the present invention, the layer thickness of the pixel is in the range from 0.1 to 100 μm, preferably it is from 1 to 50 μm, more preferably from 5 to 25 μm.
In some embodiments of the present invention, the color conversion device (100) further contains a 2nd pixel (162), preferably the device (100) contains at least said 1st pixel (161), 2nd pixel (162) and a 3rd pixel (163), more preferably said 1st pixel (161) is a red color pixel, the 2nd pixel (162) is a green color pixel and the 3rd pixel (163) is a blue color pixel, even more preferably the 1st pixel (161) contains a red light emitting moiety (110R), the 2nd color pixel (162) contains a green light emitting moiety (110G) and the 3rd pixel (163) does not contain any light emitting moiety.
In some embodiments, at least one pixel (160) additionally comprises at least one light scattering particle (130) in the matrix material (120), preferably the pixel (160) contains a plurality of light scattering particles (130).
In some embodiments of the present invention, said 1st pixel (161) consists of one pixel or two or more sub-pixels configured to emit red-color when irradiated by an excitation light, more preferably said sub-pixels contains the same light emitting moiety (110).
In a preferable embodiment, the matrix material (120) contains a (meth)acrylate polymer, preferably it is a methacrylate polymer, an acrylate polymer or a combination of thereof, more preferably it is an acrylate polymer, even more preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one acrylate monomer, further more preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one di-acrylate monomer, particularly preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one di-acrylate monomer and a monoacrylate monomer, preferably said composition is a photosensitive composition.
In some embodiments of the present invention, the height of the bank (150) is in the range from 0.1 to 100 μm, preferably it is from 1 to 50 μm, more preferably from 1 to 25 μm, furthermore preferably from 5 to 20 μm.
In a preferred embodiment of the present invention, the bank (150) is configured to determine the area of said pixel, preferably said pixel is a 1st pixel (161) or a 2nd pixel (162), and at least a part of the bank (150) is directly contacting to at least a part of the pixel, preferably said 2nd polymer of the bank (150) is directly contacting to at least a part of the 1st polymer of the 1st pixel (161).
More preferably, said bank (150) is photolithographically patterned and said 1st pixel (161) is surrounded by the bank (150), preferably said 1st pixel (161), the 2nd pixel (162) and the 3rd pixel (163) are all surrounded by the photolithographically patterned bank (150).
In another aspect, the invention also relates to a process for fabricating the composition of the present invention comprising at least, essentially consisting or consisting of, the following step Y1.
Y1) mixing at least one light emitting moiety, a reactive monomer, the chemical compound to form the composition, wherein said chemical compound comprising at least one (meth)acrylate group and another group selected from one or more of members of the group consisting of phosphine group, phosphine oxide group, phosphate group, phosphonate group, thiol group, tertiary amine group, primary amine group, carboxyl group, hetero cyclic group, silane group, sulfonic acid group, hydroxyl group, phosphonic acid group, preferably said group is a phosphate group, a phosphonate group, thiol group, primary amine group and a carboxyl group, more preferably it is a carboxyl group.
In one embodiment of the present invention, the process comprises a purification step of the light emitting moieties after mixing with the chemical compound and before adding a reactive monomer.
In a preferable embodiment of the present invention, the method comprises a purification step of the reactive monomers. More preferably, said purification step is taken place before step Y1).
More details of the composition such as “reactive monomer”, “light emitting moiety” and “chemical compound” are described above such as in the section of “reactive monomer”, “light emitting moiety” and “chemical compound”.
Additional additives as described in the section of “additional material” can be mixed.
In another aspect, the present invention also relates to a method for fabricating a color conversion device (100) of the present invention, containing at least the following steps, preferably in this sequence,
In another aspect, the present invention further relates to a color conversion device (100) obtainable or obtained from the method of the present invention.
In another aspect, the present invention further relates to use of the color conversion device (100) of the present invention in an optical device (300) containing at least one functional medium (320, 420, 520) configured to modulate a light or configured to emit light.
Further, in another aspect, the present invention further relates to an optical device (300) containing at least one functional medium (320, 420, 520) configured to modulate a light or configured to emit light, and the color conversion device (100) of the present invention.
Furthermore, as in another aspect, the present invention further relates to a new chemical compound represented by following chemical formula (IA);
As the chemical compound, for examples,
n=1 to 15, m=2 to 15,
n, m and Ra are as defined above.
n, m and Ra are as defined above.
More specifically,
Proton may be attached to carboxyl group of the specified compounds. Finally, the present invention also relates to use of the chemical compound of the present invention in a composition, preferably in a photosensitive composition.
1. A composition, preferably it is being of a photocurable composition, more preferably it is being a photocurable composition for ink-jetting, comprising at least;
2. The composition of embodiment 1, wherein said chemical compound is represented by following chemical formula (IA);
3. The composition of embodiment 1 or 2, said Rc is represented by following chemical formula:
4. The composition of any one of embodiments 1 to 3, wherein the ratio of the total weight of the chemical compound to the total weight of the light emitting moiety is in the range from 0.01 to 10, preferably it is in the range from 0.02 to 2, more preferably from 0.03 to 1; in case of said light emitting moiety is an inorganic light emitting material, the ratio of the weight of the chemical compound to the weight of the inorganic part of the inorganic light luminescent material is in the range from 0.01 to 20, preferably from 0.02 to 4, more preferably from 0.03 to 2.
5. The composition of any one of embodiments 1 to 4, wherein the light emitting moiety contains at least one ligand, preferably said ligand is different from the chemical compound, preferably said ligand comprises at least one straight-chain or branched chain alkyl group having carbon atoms 1 to 45, straight-chain or branched chain alkenyl group having carbon atoms 1 to 45 or straight-chain or branched chain alkoxyl group having carbon atoms 1 to 45, more preferably said ligand contains a saturated straight-chain or branched chain alkyl group having carbon atoms 1 to 45 or straight-chain or branched chain alkenyl group having carbon atoms 1 to 45.
6. The composition of any one of embodiments 1 to 5, wherein the average diameter of the inorganic part of the light emitting moiety is in the range from 1 nm to 18 nm, preferably it is from 2 to 15 nm, more preferably it is from 3 to 12 nm, preferably said light emitting moiety is configured to emit light having peak maximum light wavelength in the range from 400 to 900, more preferably from 500 to 850 nm, even more preferably from 510 to 820 nm.
7. The composition of any one of embodiments 1 to 6, wherein the reactive monomer is a (meth)acrylate monomer selected from a mono-(meth)acrylate monomer, a di-(meth)acrylate monomer or a tri-(meth)acrylate monomer more preferably it is a di-methacrylate monomer or a di-acrylate monomer, tri-methacrylate monomer, tri-acrylate monomer, even more preferably it is represented by following chemical formula (II);
8. The composition of any one of embodiments 1 to 7, further comprises a (meth)acrylate monomer represented by following chemical formula (I) and/or a (meth)acrylate monomer represented by following chemical formula (III);
R10 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (V)
9. The composition of any one of embodiments 1 to 8, wherein the (meth)acrylate monomer of chemical formula (II) is in the composition and the mixing ratio of the (meth)acrylate monomer of chemical formula (I) to the (meth)acrylate monomer of chemical formula (II) is in the range from 1:99 to 99:1 (formula (I):formula (II)), preferably from 5:95 to 50:50, more preferably from 10:90 to 40:60, even more preferably it is from 15:85 to 35:65, preferably at least a purified (meth)acrylate monomer represented by chemical formula (I), (II) is used in the composition, more preferably the (meth)acrylate monomer of chemical formula (I) and the (meth)acrylate monomer of chemical formula (II) are both obtained or obtainable by a purification method.
10. The composition of any one of embodiments 1 to 9, wherein the boiling point (B.P.) of said (meth)acrylate monomer of chemical formula (I) and/or chemical formula (II) is 80° C. or more, preferably it is in the range from 80° C. to 400° C., even more preferably from 85° C. to 375° C., further more preferably from 90° C. to 350° C. for large area uniform inkjet printing.
11. The composition of any one of embodiments 1 to 10, wherein said light emitting moiety is an organic light emitting moiety and/or inorganic light emitting moiety, preferably it is an inorganic light emitting moiety, more preferably it is an inorganic light emitting moiety is an inorganic phosphor or a quantum material, preferably said light emitting moiety contains a ligand attached onto the outer most surface of the light emitting moiety, more preferably said ligand is the chemical compound of embodiment 34 and/or it is at least one straight-chain or branched chain alkyl group having carbon atoms 1 to 45, straight-chain or branched chain alkenyl group having carbon atoms 1 to 45 or straight-chain or branched chain alkoxyl group having carbon atoms 1 to 45.
12. The composition of any one of embodiments 1 to 11, wherein the total amount of the light emitting moiety is in the range from 0.1 wt. % to 90 wt. % based on the total amount of the composition, preferably from 10 wt. % to 70 wt. %, more preferably from 20 wt. % to 60 wt. %.
13. The composition of any one of embodiments 1 to 12, wherein the viscosity of the composition is 35 cP or less at room temperature, preferably in the range from 1 to 35 cP, more preferably from 2 to 30 cP,
14. The composition of any one of embodiments 1 to 13, comprises an another material selected from one or more members of the group consisting of;
15. The composition of any one of embodiments 1 to 14, comprises v) scattering particles; and
16. The composition of any one of embodiments 1 to 15, the composition is configured to show the EQE value 25% or more, preferably 28% or more, even more preferably 31% or more, furthermore preferably 34% or more, and less than 50%.
17. The composition of any one of embodiments 1 to 16, wherein the composition comprises a solvent 10 wt % or less based on the total amount of the composition, more preferably it is 5 wt % or less, more preferably it is a solvent free composition, preferably the composition does not comprise any one of the following solvent selected from one or more members of the group consisting of ethylene glycol monoalkyl ethers, such as, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ethers, such as, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethylene glycol alkyl ether acetates, such as, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates, such as, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones, such as, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, such as, ethanol, propanol, butanol, hexanol, cyclo hexanol, ethylene glycol, triethylene glycol and glycerin; esters, such as, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate; and cyclic asters, such as, gamma-butyro-lactone; chlorinated hydrocarbons, such as chloroform, dichloromethane, chlorobenzene, trimethyl benzenes such as 1,3,5-trimethylbenzene, 1,2,4-trimethyl benzene, 1,2,3-trimethyl benzene, docecylbenzene, cyclohexylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 3-isopropylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl and dichlorobenzene, preferably said solvent is propylene glycol alkyl ether acetates, alkyl acetates, ethylene glycol monoalkyl ethers, propylene glycol, and propylene glycol monoalkyl ethers.
18. The composition of any one of embodiments 1 to 17, comprises at least the (meth)acrylate monomer of chemical formula (I), the (meth)acrylate monomer of chemical formula (II) and the polymer configured so that said polymer enables to the scattering particles to be dispersed in the composition, wherein the mixing ratio of the (meth)acrylate monomer of chemical formula (I):the (meth)acrylate monomer of chemical formula (II) the polymer is 1:5:0.01: to 5:4:1.
19. The composition of any one of embodiments 1 to 17, comprises at least the (meth)acrylate monomer of chemical formula (III), the (meth)acrylate monomer of chemical formula (II) and the polymer configured so that said polymer enables to the scattering particles to disperse in the composition, wherein the mixing ratio of the (meth)acrylate monomer of chemical formula (III):the (meth)acrylate monomer of chemical formula (II):the polymer is 1:5:0.01: to 5:4:1.
20. A composition comprising a polymer derived or derivable from one or more of the reactive monomers of the composition of any one of embodiments 1 to 19 and optionally one or more of scattering particles, preferably it is obtained or obtainable by curing the composition of any one of embodiments 1 to 19.
21. Process for fabricating the composition of any one of embodiments 1 to 19 comprising at least the following step Y1;
22. Use of the composition of any one of preceding embodiments, in an electronic device, optical device, sensing device or in a biomedical device or for fabricating an electronic device, sensing device, optical device or a biomedical device.
23. A layer containing the composition of embodiment 20.
24. A layer containing at least;
25. The layer of embodiment 23 or 24, wherein the layer thickness of the layer is in the range from 1 to 50 μm, preferably 5 to 15, more preferably 8 to 15, further more preferably 8-12 um.
26. The layer of any one of embodiments 23 to 26, wherein it is configured to show the EQE value 25% or more, preferably 30% or more and less than 50%.
27. Process of fabricating the layer of any one of embodiments 23 to 26, wherein the process comprises at least the following steps;
28. A layer obtained or obtainable from the process of embodiment 27.
29. A color conversion device (100) comprising at least a pixel, preferably said pixel is a 1st pixel (161) or a 2nd pixel (162), partly or fully filled with the layer of any one of embodiments 23 to 26 and 28 comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
30. The device (100) of embodiment 29, wherein the height of the bank (150) is in the range from 0.1 to 100 μm, preferably it is from 1 to 50 μm, more preferably from 1 to 25 μm, furthermore preferably from 5 to 20 μm.
31. The device (100) of embodiments 29 or 30, wherein the layer thickness of the pixel (161) is in the range from 0.1 to 100 μm, preferably it is from 1 to 50 μm, more preferably from 5 to 25 μm.
32. Use of the composition of any one of embodiments 1 to 19 for fabricating the layer of any one of embodiments 23 to 26, 28 or the device (100) of any one of embodiments 29 to 31
33. An optical device (300) containing at least one functional medium (320, 420, 520) configured to modulate a light or configured to emit light, and the color conversion device (100) of any one of embodiments 29 to 31.
34. A chemical compound represented by following chemical formula (IA);
35. Use of the chemical compound of embodiment 34 in a composition, preferably in a photosensitive composition.
Improved homogeneous dispersion of light emitting moieties in the composition, improved homogeneous dispersion of scattering particles in the composition, preferably improved homogeneous dispersion of both light emitting particles and scattering particles, more preferably improved homogeneous dispersion of light emitting moieties and/or scattering particles without solvent; composition having lower viscosity suitable for inkjet printing, no increasement with time of viscosity of composition, preferably a composition which can keep lower viscosity even if it is mixed with high loading of light emitting moieties and/or scattering particles, even more preferably without solvent; composition having lower vapor pressure for large area uniform printing; a new composition realizing no residue around ink jet printing nozzle during/after ink jet printing, improved QY and/or EQE of light emitting moieties in the composition, improved QY and/or EQE of light emitting moieties after printing; improved thermal stability; easy printing without clogging at a printing nozzle; easy handling of the composition, improved printing properties; simple fabrication process; improved absorbance of blue light; improved solidity of a later made from the composition after inkjet printing.
The working examples below provide descriptions of the present invention, as well as an in-detail description of their fabrication. However, the present invention is not necessary to be limited to the working examples.
In absence of light, into 1 L 3-neck round bottom flask equipped with stir bar, within soft heating mantle and thermocouple, chiller (5° C.) circulation, under Ar: Poly(propylenglycol)acrylate (10.20 gr), BHT (46 mg), succinic anhydride (2.56 gr) and DMAP (0.13 gr) in anhydrous toluene (520 mL) are stirred together. Reaction heated to reflux (111° C.) overnight under argon.
On the next day, the mixture is cooled down to RT, and extracted with distilled water, then with brine. Organic phase is dried over MgSO4, filtered via filter paper, then volatiles is removed under reduced pressure on Rotavap.
The residue is purified using silica gel (200-425 mesh) chromatography with CHCl3 followed by CHCl3/CH3OH (97/3). Fractions are collected, volatiles removed. Each fraction is analyzed by 1H NMR and DOSY. Then compound L1 is obtained.
Derivatives of L1 having repeating unit 3-5 instead of 7 repeating unit of L1 (a shorter analogues with 3-5 repeating units compared to L1) are successfully synthesized in the same manner as described in preparation example 1.
Another derivatives to L1 can also be synthesized by changing the reactants, amounts of the reactants with general knowledge based on the synthesis process described in preparation example 1 mentioned above, for examples, alcohols comprising (meth)acrylate group, branched or linear alkoxylene group, branched or linear saturated alkylene group, branched or linear unsaturated alkylene group and be used, any derivative of succinic anhydrate can be used.
To 0.04 g of Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irganox™819) as photo initiator is added 2.368 g of LA and 0.592 g of HDDA. The mixture is shaken until complete dissolution of Irganox™819.
To 0.04 g of Irganox™819 is added 1.580 g of LA and 0.380 g of HDDMA. The mixture is shaken until complete dissolution of Irganox™819.
0.75 g of matrix obtained in example 1, 0.25 g of InP based Red QDs having ZnSe/ZnS double shell layers dispersed in heptane are mixed in a glass flask and volatiles are evaporated on rotary evaporator under vacuum at 30 deg. C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line.
0.03 g of linoleic acid and 0.25 g of InP based Red QDs having ZnSe/ZnS double shell layers dispersed in heptane are mixed and heated to 40 deg. C. for 2 hours. Then 0.66 g of matrix obtained in example 1 is added, volatiles are evaporated on rotary evaporator under vacuum at 30 deg. C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.06 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 1 is obtained.
0.06 g of compound L1 is dissolved in 1 mL of toluene, then mixed with 0.25 g of InP based Red QDs having ZnSe/ZnS double shell layers dispersed in heptane and heated to 40 deg. C. for 1 hour. Then 0.63 g of matrix obtained in example 1 is added, volatiles are evaporated on rotary evaporator under vacuum. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.06 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 2 is obtained.
1.17 g of InP based Red QDs having ZnSe/ZnS double shell layers dispersed in 5.1 mL of heptane are put in a glass flask, 5 mL of anhydrous toluene are added, 0.503 g of compound L1 are added, the mixture is flashed with Ar and heated to 40 deg. C. for 1 hour under Ar. After cooling down the solution, the red QDs are precipitated out by adding 96 ml of dry heptane. Then the turbid solution is centrifuged at 2950 G for 5 min, and supernatant is decanted. Then 10 mL of dry toluene are added to prepare stock solution in toluene.
0.35 g of Red QDs obtained in example 4 dispersed in toluene are mixed with 0.59 g of matrix obtained in example 1, volatiles are evaporated on rotary evaporator under vacuum. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.06 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 3 is obtained.
0.2 g of InP based Green QDs having ZnSe/ZnS double shell layers (OD/mg=0.34) dispersed in toluene are mixed with 0.27 g of matrix obtained in working example 2, volatiles are evaporated on rotary evaporator under vacuum. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.03 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 4 is obtained.
0.2 g of InP based Green QDs having ZnSe/ZnS double shell layers (OD/mg=0.71) dispersed in toluene are mixed with 0.27 g of matrix obtained in working example 2, volatiles are evaporated on rotary evaporator under vacuum. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.03 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 5 is obtained.
0.20 g of InP based Green QDs having ZnSe/ZnS double shell layers (OD/mg=0.34) dispersed in toluene are mixed with 0.22 g of matrix obtained in working example 2, volatiles are evaporated on rotary evaporator under vacuum. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.05 g of AES is added; the resulting mixture is mixed on shaker at >360 RPM for at least 30 min. Then 0.03 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 6 is obtained.
0.20 g of InP based Green QDs having ZnSe/ZnS double shell layers (OD/mg=0.71) dispersed in toluene are mixed with 0.22 g of matrix obtained in working example 2, volatiles are evaporated on rotary evaporator under vacuum. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Then 0.05 g of AES is added; the resulting mixture is mixed on shaker at >360 RPM for at least 30 min. Then 0.03 g of TiO2 dispersed in octane is added. Volatiles are removed under vacuum of 60 mTorr on a Schlenk line. Finally, the QD ink composition 7 is obtained.
Film A with 15 μm thickness is fabricated using the QD ink composition 1 obtained in the comparative example 2 by filling glass sandwich test cell with the QD ink composition 1. Then QD ink composition inside the glass cell is cured under argon at 2.3 mW/cm2 for 10 min In the same manner as described above, Films B, C, D, E, F, G are fabricated with using the QD ink compositions 2 to 7 instead of the QD ink composition 1.
EQE measurement of the films A to F is carried out by using integrating sphere equipped with excitation light by optical fiber (CWL: 450 nm) and spectrometer (Compass X, BWTEK). To detect the photons of the excitation light, air is used as a reference at room temperature.
The number of photons of light emission from the test cell towards the integrating sphere is counted by the spectrometer at room temperature. EQE is calculated by the following calculation Method.
EQE=Photons[Emission light]/Photons[Excitation light measured without sample in place]
Following table 1 show the results of the measurements.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21194784.1 | Sep 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/074140 | 8/31/2022 | WO |
