Patent Application
20240309269
The present invention relates to a photo-reactive composition comprising at least one light emitting moiety, a layer, a color conversion device, process for fabricating a color conversion device, an optical device containing at least one color conversion device, method for fabricating a color conversion device and use of a composition.
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 vaper 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 inventors aimed to solve one or more of the above-mentioned problems.
Then it is found a novel composition, preferably it is being of a photocurable composition, comprising at least;
In another aspect, the present invention relates to a composition, preferably it is being of a photocurable composition, comprising at least;
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.
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 steps Y1 and Y2, preferably in this sequence or Y3;
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;
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 1st pixel (161) 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, 420, 520) 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, 420, 520) configured to modulate a light or configured to emit light, and the color conversion device (100) of the present invention.
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;
In another aspect, the present invention relates to a composition, preferably it is being of a photocurable composition, comprising at least;
In a preferred embodiment of the present invention, the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand to the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound satisfies the following formula (Q), preferably said chain contains at least one carbon-carbon double bond, more preferably said chain contains 1 to 5 carbon-carbon double bonds, more preferably 1 to 3 carbon-carbon double bonds, even more preferably 1 to 2 carbon-carbon double bonds.
The number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand <the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound-(Q)
Preferably the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound is 1 to 20 larger than the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand, more preferably it is 3 to 15 larger, more preferably 5 to 12 larger, even more preferably said group contains at least one carbon-carbon double bond, furthermore preferably the position of said at least one carbon-carbon double bond in the group of the chemical compound is positioned outer side (—CH3 terminal side of the group) than the ch3 terminal of the ligand. In other words, the length of the group of the chemical compound is longer than the length of the group of the ligand, preferably the position of said at least one carbon-carbon double bond in the group of the chemical compound is in the outer (longer) side of the edge of the group of the ligand.
It is believed that longer length of the chemical compound leads improved dispersibility of the light emitting moiety and/or scattering particles. If carbon-carbon double bond is placed outer side (longer side) from the edge of the ligand, it makes it makes steric effects of the chemical compounds, then alkyl group, the alkenyl group, the alkoxy group of the chemical compounds can be dispersed (not aligned in the same direction). Then, it may lead good compatibility/interaction with reactive monomers.
It is believed that the chemical compound is preferable to control viscosity/solubility of the composition accrodingly. More preferably it can prevent increasement of visicosity of the composition and/or keeping a good solubility of the light luminescent moietys in a long term storage in the composition.
Further, it is believed that one or more of carbon-carbon double bonds in the chain may lead lower viscosity and improved dispersibility of light emitting moiety and/or scattering particles 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, 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, a carboxyl group or a combination of any of these, more preferably it is a carboxyl group.
It is believed that a phosphonate group, thiol 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, the chemical compound is represented by following chemical formula (XA).
Z—Y (XA)
wherein
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 0.6:40 to 1:3, preferably it is from 1:40 to 1:2, more preferably from 1.5:40 to 1:1; 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 0.003 to 3.2, preferably from 0.006 to 2.8, more preferably from 0.015 to 1.3.
It is believed that said weight ratio of the chemical compound is very preferable to control viscosity/solubility of the composition accrodingly. And it is very preferable to prevent increasement of visicosity of the composition and/or keeping a good solubility of the light luminescent moietys in a long term storage in the composition.
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 250° C. or more, preferably it is in the range from 250° C. to 350° C., even more preferably from 280° C. to 350° C., further more preferably from 300° C. to 348° 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 (III) having the viscosity value of 25 cP or less at 25° C. and the boiling point at least 250° C. or more, preferably it is in the range from 250° C. to 350° C., more preferably from 300° C. to 348° 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. II. 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 (III) 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 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);
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 250° C. or more, preferably the (meth)acrylate monomers of chemical formula (I) and chemical formula (II) are both 250° C. or more, more preferably it is in the range from 250° C. to 350° C., even more preferably from 280° C. to 350° C., further more preferably from 300° C. to 348° C.
In a preferred embodiment of the present invention, 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, even more preferably from 2 to 25 cP.
According to the present invention, said viscosity can be measured by vibration type viscometer VM-10A (SEKONIC) at room temperature. https://www.sekonic.co.jp/english/product/viscometer/vm/vm_series.html
Furthermore preferably, said R3 of formula (I) and R4 of formula (I) are, each independently of each other, selected from the following groups, wherein the groups can be substituted with Ra, preferably they are unsubstituted by Ra.
Particularly preferably, said R3 and R4 of formula (I) are, at each occurrence, independently or differently, selected from the following groups.
wherein “*” represents the connecting point to oxygen atom of the formula or the connecting point to X2 of the formula in case of R3, and wherein “*” represents the connecting point to oxygen atom of the formula or the connecting point to X1 of the formula in case of R4.
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: 314° C.).
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 250° C. or more, preferably the (meth)acrylate monomer of chemical formula (II) is 250° C. or more, more preferably it is in the range from 250° C. to 350° C., even more preferably from 280° C. to 350° C., further more preferably from 300° C. to 348° 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 250° C. or more, preferably the (meth)acrylate monomers of chemical formula (I) and chemical formula (II) are both 250° C. or more, more preferably it is in the range from 250° C. to 350° C., even more preferably from 280° C. to 350° C., further more preferably from 300° C. to 348° 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, wherein the groups can be substituted with Ra, preferably they are unsubstituted by Ra.
wherein “*” represents the connecting point to R6 of X3 in case I is 1, and it is representing the connecting point to oxygen atom of X3 of the formula (II) in case n is 0.
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 (II) to the total amount of the (meth)acrylate monomer of chemical formula (I) 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 its solidity of a later made from the composition after inkjet printing.
According to the present invention, a publicly known a (meth)acrylate monomer represented by following chemical formula (III) can be used to improve solidity of a 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 95%.
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;
According to the present invention, in a preferred embodiment, 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, even more preferably from 2 to 25 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, 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, 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)
wherein R12 is a hydrogen atom, a straight or a branched alkyl group having 1 to 30 carbon atoms, or an aryl group having 1 to 30 carbon atoms; R13 is a hydrogen atom, a straight or a branched alkyl group having 1 to 30 carbon atoms, or an aryl group having 1 to 30 carbon atoms; R12 and R13 can be same or different of each other; R14 is a single bond, a straight or a branched alkylene group having 1 to 30 carbon atoms, alkenylene group having 1 to 30 carbon atoms, (poly)oxaalkylene group having 1 to 30 carbon atoms.
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)
wherein the symbol “A” represents a repeating unit A; the symbol “B” is taken to mean the repeating unit B; the symbols “n”, “m”, and “o” are at each occurrence, independently or dependently of each other, integers 1 to 100, preferably 5 to 75, more preferably 7 to 50; even more preferably the repeating unit B comprises a polymer chain selected from the group consisting of (poly)ethylene, (poly)phenylene, polydivinylbenzene, (poly)ethers, (poly)esters, (poly)amides, (poly)urethanes, (poly)carbonates, polylactic acids, (poly)vinyl esters, (poly)vinyl ethers, polyvinyl alcohols, polyvinylpyrrolidones, celluloses and derivatives of any of these.
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),
wherein the chemical formula (X), R15 is hydrogen atom, or methyl group; R16 is alkyl group having 1 to 10 carbon atoms; and n is an integer 1 to 5, “*” represents the connecting point to an another polymer repeating unit or a terminal of the polymer.
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 semiconducting light emitting nanoparticle.
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 2,000 g/mol, more preferably from 400 g/mol to 1,000 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-Ald 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 10:89:1 to 50:40:10, preferably in the range from 15:82:3 to 30:60:10.
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 10:89:1 to 50:40:10, preferably in the range from 15:82:3 to 30:60:10.
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, Al2O3 TiO2, 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 4 wt % or less based on the total amount of the solid contents of the layer, preferably it is in the range from 4 to 0 wt %, more preferably it is in the range from 1 to 0 wt %, more preferably the layer and/or the composition does not contain any scattering particles.
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 95%.
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 the 1st pixel (161), preferably from 10 wt. % to 70 wt. %, more preferably from 30 wt. % to 50 wt. %.
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 the longest axis of the semiconducting nanosized light emitting particles.
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 the 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)
wherein 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, preferably 0≤x≤1, 0≤y≤1, z=0, and x+y=1, preferably, the shell layer is ZnSe, ZnSxSey, ZnSeyTez or ZnSxTez.
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′)
wherein 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, preferably, the shell layer is ZnSe, ZnSxSey, ZnSeyTez, or ZnSxTez with the proviso that the shell layer and the 2nd shell layer is not the same.
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 30 wt. % to 50 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, Dedecyl amine (DDA), Tetradecyl amine (TDA), Hexadecyl amine (HDA), and Octadecyl amine (ODA), Oleylamine (OLA), 1-Octadecene (ODE), thiols such as hexadecane 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 PEG thiol (mPEG-thiol) or a derivatives of mPEG thiol 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 μm.
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 1st pixel (161) partly or fully filled with the layer of any one of claims 20 to 22 and 24 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 1st pixel (161) comprises at least a matrix material (120) containing a light emitting moiety (110). In a preferable embodiment, the 1st pixel (161) 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 (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.
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 1st pixel (161) and at least a part of the bank (150) is directly contacting to at least a part of the 1st pixel (161), 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 steps Y1 and Y2, preferably in this sequence or Y3;
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) and/or Y0).
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.
1. A composition, preferably it is being of a photocurable composition, comprising at least;
2. A composition, preferably it is being of a photocurable composition, comprising at least;
3. The composition of embodiment 2, wherein the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand to the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound satisfies the following formula (Q), preferably said chain contains at least one carbon-carbon double bond, more preferably said chain contains 1 to 5 carbon-carbon double bonds, more preferably 1 to 3 carbon-carbon double bonds, even more preferably 1 to 2 carbon-carbon double bonds.
The number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand <the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound—(Q)
Preferably the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound is 1 to 20 larger than the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand, more preferably it is 3 to 15 larger, more preferably 5 to 12 larger, even more preferably said group contains at least one carbon-carbon double bond, furthermore preferably the position of said at least one carbon-carbon double bond in the group of the chemical compound is positioned outer side (—CH3 terminal side of the group) than the ch3 terminal of the ligand. In other words, the length of the group of the chemical compound is longer than the length of the group of the ligand, preferably the position of said at least one carbon-carbon double bond in the group of the chemical compound is in the outer (longer) side of the edge of the group of the ligand.
4. The composition of any one of embodiments 1 to 3, wherein 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, 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, a carboxyl group or a combination of any of these, more preferably it is a carboxyl group.
5. The composition of any one of embodiments 1 or 4, wherein the chemical compound is represented by following chemical formula (XA).
Z—Y (XA)
6. The composition of any one of embodiments 1 to 5, wherein the ratio of the total weight of the chemical compound to the total weight of the light emitting moiety is in the range 0.6:40 to 1:3, preferably it is from 1:40 to 1:2, more preferably from 1.5:40 to 1:1; 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 0.003 to 3.2, preferably from 0.006 to 2.8, more preferably from 0.015 to 1.3.
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);
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 250° C. or more, preferably the (meth)acrylate monomers of chemical formula (I) and chemical formula (II) are both 250° C. or more, more preferably it is in the range from 250° C. to 350° C., even more preferably from 280° C. to 350° C., further more preferably from 300° C. to 348° C.
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 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 and the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand to the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound satisfies the following formula (Q).
The number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the ligand <the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group of the chemical compound—(Q)
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 15 wt. % to 50 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, even more preferably from 2 to 25 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
16. The composition of any one of embodiments 1 to 15, the composition is configured to show the EQE value 23% or more, preferably 24% or more and less than 95%.
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 10:89:1 to 50:40:10, preferably in the range from 15:82:3 to 30:60:10.
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 10:89:1 to 50:40:10, preferably in the range from 15:82:3 to 30:60:10.
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, preferably it is obtained or obtainable by curing the composition.
21. Process for fabricating the composition of any one of embodiments 1 to 19 comprising at least the following steps Y1 and Y2, preferably in this sequence or Y3;
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 a 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 μm.
26. Process of fabricating the layer of any one of embodiments 23 to 25, wherein the process comprises at least the following steps;
27. A layer obtained or obtainable from the process of embodiment 26.
28. A color conversion device (100) comprising at least a 1st pixel (161) partly or fully filled with the layer of any one of embodiments 23 to 25 and 27 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).
29. The device (100) of embodiment 28, 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.
30. The device (100) of embodiment 28 or 29, 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.
31. The device (100) of any one of embodiments 28 to 30, 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.
32. The device (100) of any one of embodiments 28 to 31 wherein 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).
33. The device (100) of any one of embodiments 28 to 32, wherein 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).
34. The device (100) of any one of embodiments 28 to 33, wherein the bank (150) is configured to determine the area of said 1st pixel (161) and at least a part of the bank (150) is directly contacting to at least a part of the 1st pixel (161), 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).
35. The device (100) of any one of embodiments 28 to 34, wherein 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).
36 Use of the composition of any one of embodiments 1 to 19 for fabricating the layer of any one of embodiments 23 to 25, 27 or the device (100) of any one of embodiments 28 to 35.
37. Method for fabricating a color conversion device (100) of any one of embodiments 28 to 35 containing at least the following steps, preferably in this sequence;
38. The color conversion device (100) obtainable or obtained from the method of embodiment 37.
39. 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 28 to 35.
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 vaper 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 1-7 below provide descriptions of the present invention, as well as an in-detail description of their fabrication.
15.79 g of TiO2 in n-octane is mixed with 38.00 g of LA in a glass flask and n-octane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg·C. Thus obtained the 20 wt. % TiO2 stock in LA.
1,6-Hexanediol diacrylate (HDDA) and lauryl acrylate (LA) are stored over molecular sieves prior to use.
1.500 g of TiO2 stock in LA from working example 1, 1.956 g of LA, 0.774 g of HDDA, 5.000 g of InP based red QD in n-heptane and 0.180 g of erucic acid are mixed in a glass flask. The mixture is stirred at 40 deg·C for 2 hours under N2 atmosphere, then n-heptane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg·C. To this mixture, 0.060 g of Omnirad™ 819 and 0.030 g of Irganox™ 1010 are added and the mixture is stirred at room temp. until the ink becomes homogeneous, thus obtained the red QD ink of the composition shown in the table below.
1.500 g of TiO2 stock in LA from working example 1, 1.956 g of LA, 0.774 g of HDDA, 5.000 g of InP based red QD in n-heptane and 0.180 g of nervonic acid are mixed in a glass flask. The mixture is stirred at 40 deg·C for 2 hours under N2 atmosphere, and then n-heptane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg·C. To this mixture 0.060 g of Omnirad™ 819 and 0.030 g of Irganox™ 1010 are added and the mixture is stirred at room temp. until the ink becomes homogeneous, thus obtained the red QD ink of the composition shown in the table below.
4.886 g of InP based red QD in n-heptane and 0.180 g of erucic acid are mixed in a glass flask and the mixture is stirred at 40 deg. C for 2 hours under N2 atmosphere. To the mixture 1.750 g of TiO2 stock in LA obtained in example 1, 0.930 g of LA, 0.565 g of HDDA are added, and then the solvents in the mixture is evaporated by rotary evaporator under vacuum at 40 deg·C. To this mixture 0.050 g of Omnirad819 and 0.025 g of Irganox1010 are added and the mixture is stirred at room temp. until the ink becomes homogeneous, thus obtained the red QD ink of the composition shown in the table below.
Nozzle plate wetting test is performed as described below.
QD ink obtained in working example 2 is dropped onto a nozzle plate of print head (Dimatix DMP-2831 material printer, Fuji film), then the dropped ink is removed by soaking up with the cleaning pad. Cleanness of the surface on the nozzle plate is observed by eyes.
The QD ink is well repelled on the nozzle plate. The surface of nozzle plate is very clean after cleaning by the pad. It indicates that during ink jet printing, the ink composition of the present invention can be smoothly ink jetted onto a substrate without causing clogging, without remaining around nozzle of ink jet machine, without remaining on or around the surface of nozzle.
15.79 g of TiO2 in n-octane is mixed with 38.00 g of LA in a glass flask and n-octane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg·C. Thus obtained the 20 wt. % TiO2 stock in LA.
6.0 g of InP based Red QDs in heptane are put in a glass flask, then heptane is evaporated by rotary evaporator under vacuum at 40 deg·C. The dried QDs are dissolved in 12.6 ml of anhydrous THF and to the solution, 0.4 ml of oleic acid is added. The mixture is heated to reflux under N2 atmosphere for 2 hours. After cooling down the solution, the red QDs are precipitated out by adding 60 ml of dry acetone. Then the turbid solution is centrifuged at 6,000 G for 5 min. and supernatant is decanted. By complete dryness of the pellets under vacuum 1.23 g of the purified red QD powder is obtained. This purified red QD powder is dissolved in 3.51 g of dry n-octane to prepare 26 wt. % stock solution in n-octane.
0.910 g of TiO2 stock in LA obtained in reference example 1-1, 1.274 g of LA, 0.491 g of HDDA, 3.500 g of red QD in n-octane obtained in reference example 1-2 are mixed in a glass flask and n-octane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg. C. To this mixture 0.036 g of Omnirad819 and 0.018 g of Irganox1010 are added and the mixture is stirred at room temp. until the ink became homogeneous, thus obtained the red QD ink of the composition shown in the table below.
Nozzle plate wetting test is performed as described below.
QD ink obtained in reference example 3 is dropped onto a nozzle plate of print head (Dimatix DMP-2831 material printer, Fuji film), then the dropped ink is removed by soaking up with the cleaning pad. Cleanness of the surface on the nozzle plate is observed by eyes.
Residue of QD ink remains on the surface of nozzle plate after cleaning.
QD ink obtained in working example 2 is injected into a test cell with 10 μm gap.
Then the obtained 6 test cells containing QD ink A is cured by applying UV light irradiation with different curing time conditions each other to make a cured ink in the test cell.
EQE measurement is carried out by using integrating sphere equipped with excitation light by optical fiber (CWL: 450 nm) and spectrometer (USB4000, Ocean Optics). 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 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]
As a result, EQE value 32.7% is obtained.
The red QD ink obtained in working example 2 and the red QD ink obtained in reference example 3 are stored in an atmospheric condition at room temperature.
The red QD ink of working example 2 (QD with erucic acid) shows excellent dispersibility compared to the red QD with oleic acid or without any additive ligand.
In the red QD ink with erucic acid, the QDs are perfectly dispersed for at least one month in the monomer mixture in presence of TiO2 particles. On the other hand the red QD ink with oleic acid of reference example 3 produces some precipitates after 1 week and the red QDs without additive ligand do not completely disperse in the acylate monomer mixture even without TiO2 particles.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21158080.8 | Feb 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/053719 | 2/16/2022 | WO |
