Patent Application
20240002688
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.
Preventing/reducing long term viscosity increase of ink composition, Achieving higher cross-linking density, realizing good compatibility of (meth)acrylate monomers, selecting publically available (meth)acrylate monomers, realizing lower vaper pressure and higher boiling point, achieving a solid film with high polymerization efficiency by QD containing acrylate ink realising an improved solidity of the film derived by (meth)acrylate monomers under short time and week UV curing condition,
Realizing improved optical properties of bank, improved compatibility between a bank and a composition containing a light emitting moiety (e.g. QD ink), improved wetting properties and chemical stability towards a composition containing a light emitting moiety, less degradation of the bank structure upon bringing the composition containing a light emitting moiety into contact with the bank,
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, 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 another aspect, the present invention relates to a composition comprising at least a polymer derived or derivable from the (meth)acrylate 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, the descriptions such as “Cx-y”, “CxCy” and “Cx” mean the number of carbons in the molecule or substituent group. For example, C1-6 alkyl means alkyl having 1 to 6 carbons (such as methyl, ethyl, propyl, butyl, pentyl and hexyl). Further, the fluoroalkyl as used in the present specification refers to one in which one or more hydrogen in alkyl is replaced with fluorine, and the fluoroaryl is one in which one or more hydrogen in aryl are replaced with fluorine.
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.
In the present specification, “%” represents mass % and “ratio” represents ratio by mass.
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, essentially consisting of or consisting of;
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).
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.
In a preferred embodiment of the present invention, said chemical compound further comprises at least one straight-chain or branched alkyl group having carbon atoms 1 to 45, straight-chain or branched alkenyl group having carbon atoms 1 to 45 or straight-chain or branched alkoxyl group having carbon atoms 1 to 45, preferably said carbon atoms of the alkyl group, the alkenyl group and/or the alkoxy group are in the range from 5 to 35, more preferably it is from 10 to 25, even more preferably from 12 to 24, furthermore preferably it is from 14 to 20 and preferably said alkyl group, alkenyl group and/or alkoxy group may be substituted or unsubstituted.
It is believed that it is preferable to control viscosity/solubility 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 moietys in a long term storage in the composition.
More preferably, the chemical compound is represented by following chemical formula (XA).
Z—Y (XA)
wherein
where “*” represents the connecting point to symbol Y of the formula, Rx1 is a 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 phosphonate group, thiol group, a carboxyl group or a combination of any of these, more preferably it is a carboxyl group; and
Preferable embodiments of the chemical compound can be selected from stearic acid, oleic acid, parmitic acid, dodecenoic acid, octadecylphosphonic acid, hexylphosphonic acid, monostearyl phosphate, didodecyl phosphate, monododecyl phosphate, didodecyl phosphate, their derivatives and a combination of any of these.
In a preferable 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 accordingly. And it is very preferable to prevent increasement of viscosity of the composition and/or keeping a good solubility of the light luminescent moietys in a long term storage in the composition.
According to the present invention, the composition, comprises at least i) one (meth)acrylate monomer represented by following chemical formula (I) together with ii) a light emitting moiety and iii) the chemical compound.
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
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 (meth)acrylate monomer of chemical formula (I) 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 (meth)acrylate monomer of formula (I) 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.
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), https://www.sigmaaldrich.com/chemistry/solvents/learning-center/nomograph.html.
According to the present invention, any types of publicly available acrylates and/or methacrylates represented by chemical formula (I) 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) can be used.
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 (BP:342° C.), HDDMA (BP:307) or DPGDA (BP: 314° C.).
In some embodiments of the present invention, the composition further comprises another (meth)acrylate monomer represented by following chemical formula (II);
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.).
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.
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.
In some embodiments of the present invention, the composition further comprises a (meth)acrylate monomer represented by following chemical formula (III);
wherein R9 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (IV)
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.
In another aspect, present invention also relates to a novel composition, preferably it is being of a photocurable composition, comprises at least;
It is believed that said (meth)acrylate monomer represented by chemical formula (III), especially TMPTA, is preferable due to [1] high cross-linking density even with small loading [2] compatibility to the (meth)acrylate monomer represented by Chemical formula (II), especially to LA, [3] publical availability, [4] lower vaper pressure and [5] higher boiling point of the monomer. Regarding [1], acryl group as reactive group is preferably selected because acrylate has higher reaction speed than (meth)acrylate and other double bond structures. QD containing acrylate ink can achieve solid film with high polymerization efficiency by selecting said monomer of chemical formula (III). It is also believed solidity of the film derived by said (meth)acrylate monomer represented by chemical formula (III) and (meth)acrylate monomer represented by chemical formula (II) is preferable even if the printed composition containing a (meth)acrylate monomer represented by chemical formula (III) and a (meth)acrylate monomer represented by chemical formula (II) is cured under short and week UV curing condition.
In a preferable embodiment, the mixing ratio of the (meth)acrylate monomer of chemical formula (III) to the (meth)acrylate monomer of chemical formula (II) is in the range from 1:99 to 99:1 (formula (III):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 (III), (II) is used in the composition, more preferably the (meth)acrylate monomer of chemical formula (III) and the (meth)acrylate monomer of chemical formula (II) are both obtained or obtainable by a purification method.
According to the present invention, 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;
EQE=Photons [Emission light]/Photons [Excitation light measured without sample in place];
BL=Photons [measured without sample in place]/Photons [Excitation light measured without sample in place];
Emission light if green light emitting moieties are used: 480 nm-600 nm,
Emission light if red light emitting moieties are used: 560 nm-680 nm
Excitation light: 430 nm-470 nm.
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.
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, 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-AId 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 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, 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 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 http://pslc.ws/macroq/dsc.htm; 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. %.
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, AISb, 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.
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. %.
Ligands
In some embodiments of the present invention, optionally, the semiconducting light emitting nanoparticle 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.
Use of the Composition
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 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.
Color Conversion Device (100)
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).
1st Pixel (161)
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).
Matrix Material (120)
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 mono-acrylate monomer, preferably said composition is a photosensitive composition.
Bank (150)
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).
Polymer Material of the Bank
In a preferred embodiment of the present invention, said polymer material of the bank is a thermosetting resin, preferably it is a photosensitive resin, more preferably it is a thermosetting and photosensitive resin containing an alkaline soluble polymer, preferably the weight-average molecular weight of said alkaline soluble polymer is in the range from 1,000 to 100,000, more preferably it is from 1,200 to 80,000, preferably the solid-acid value of the alkaline soluble polymer is in the range from 10 to 500 mg KOH/g, more preferably it is from 20 to 300 mg KOH/g, preferably said alkaline soluble polymer is selected from (meth)acrylate polymer, siloxane (meth)acrylate polymer, more preferably it is a methacrylate polymer, an acrylate polymer or a combination of thereof, even more preferably the polymer material is an acrylate polymer, further more preferably said bank (150) is obtained or obtainable from a bank composition containing at least one alkaline soluble polymer and a chemical compound containing at least two (meth)acryloyloxy groups, particularly preferably said bank (150) is obtained or obtainable from a bank composition containing at least one alkaline soluble polymer and a chemical compound containing at least two (meth)acryloyloxy groups and a surfactant, preferably said composition is a photosensitive composition, preferably said bank is a cured layer obtained or obtainable from the composition, more preferably said bank is a photolithographically patterned cured layer obtained or obtainable from the composition.
Surfactant of the Bank
According to the present invention, preferably said bank (150) further contains a surfactant, preferably at least a part of the surface of the bank is covered by said surfactant, more preferably the surface of the bank is hydrophobic, even more preferably the surface of the top part of the bank is oil-repellent, preferably the total amount of the surfactant is in the range from 0.001 to 5 wt. %, more preferably from 0.01 to 4 wt. %, even more preferably from 0.05 to 3 wt. %, furthermore preferably from 0.1 to 1 wt. % based on the total amount of the bank.
In a further preferable embodiment, the bank (150) contains a nonionic surfactant, preferably said nonionic surfactant is a hydrocarbon based nonionic surfactant, fluorine-based nonionic surfactant, organosilicon based nonionic surfactant or a combination of these, more preferably said hydrocarbon based nonionic surfactant is selected from one or more members the group consisting of polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diester; polyoxyethylene fatty acid monoester; polyoxyethylene polyoxypropylene block polymer; acetylene alcohol; acetylene glycol such as 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 2,5-di-methyl-3-hexyne-2,5-diol, 2,5-di-methyl-2,5-hexanediol; polyethoxylate of acetylene alcohol; acetylene glycol derivatives, such as polyethoxylate of acetylene glycol; preferably fluorine-based nonionic surfactant is selected from one or more of fluorine-containing surfactants; preferably said hydrocarbon based nonionic surfactant is selected from organosiloxane surfactants, preferably the surfactant is a fluorine-based nonionic surfactant.
Saccharide in the Bank
In a preferred embodiment of the present invention, the bank (150) further contains a saccharide, preferably said saccharide is selected from a monosaccharide, an oligosaccharide, a polysaccharide or a mixture of thereof, more preferably it is an oligosaccharide, even more preferably said saccharide is an oligosaccharide formed by dehydrating and condensing 2 to 10 molecules of a monosaccharide, and also includes a cyclic oligosaccharide (for example, cyclodextrin), furthermore preferably it is cyclodextrin or disaccharide obtained by condensing two molecules of monosaccharide, even more probably it is a disaccharide obtained by condensing two molecules of monosaccharide, furthermore preferably the saccharide is oligosaccharide having an alkylene oxide having 1 to 6 carbon atoms, more preferably it has an alkylene oxide having 2 to 5 carbon atoms, and further preferably it has an ethylene oxide or propylene oxide, particular preferably it is sucrose-alkyleneoxide-lauricacid ester, preferably the total amount of the surfactant is in the range from 0.001 to 1 wt. %, more preferably from 0.1 to 60 wt. %, even more preferably from 1 to 40 wt. %, furthermore preferably from 10 to 30 wt. % based on the total solid contents of the polymer material. For examples, sucrose ethylene oxide adduct can be used preferably.
Colorant in the Bank
In a preferable embodiment of the present invention, the bank (150) further comprises a colorant, preferably said colorant is an organic colorant and/or an inorganic colorant, more preferably it is a black colorant selected from an organic black pigment and/or inorganic black pigment, preferably said black colorant has a light transmittance ratio represented by [light transmittance at the wavelength of 365 nm]/[light transmittance at the wavelength of 500 nm] of 1.2 or more, more preferably the ratio is 2.0 or more, preferably said black colorant has a light transmittance ratio represented by [light transmittance at the wavelength of 365 nm]/[light transmittance at the wavelength of 500 nm] of 5.0 or less, even more preferably it is in the range from 1.2 to 5.0, further more preferably it is from 2.0 to 4.0 provided that the transmittance is obtained by measuring a film obtained by the following steps: applying a composition in which 10 mass % of a black colorant is dispersed based on the total amount of the resin forming a film having a film thickness of 10 μm by applying said composition to a glass substrate, and curing at 100° C., then the obtained film is measured using UV-vis-NIR (Hitachi High-Technologies Corporation), preferably said inorganic black pigment is zirconium nitride, preferably said organic black pigment is a mixture of two or more organic color pigments, more preferably it is a mixture of red, green blue organic color pigments configured to show black color by mixing, further more preferably said organic black pigment is a mixture selected from the group consisting of an azo type, a phthalocyanine type, a quinacridone type, a benzimidazolone type, an isoindolinone type, a dioxazine type, an indanthrene type and a perylene type organic pigments, particularly preferably said organic black pigment is a mixture of one selected from the group consisting of C. I. Pigment Orange 43, C. I. Pigment Orange 64 and C. I. Pigment Orange 72, with C. I. Pigment Blue 60, C. I. Pigment Green 7, C. I. Pigment Green 36 and C. I. Pigment Green 58.
Preferably, the total amount of said colorant is 3 to 80 wt. %, preferably 5 to 50 wt. % based on the total amount of the polymer material of the bank.
Supporting Medium (170)
In some embodiments of the present invention, said supporting medium (170) is a substrate, more preferably it is a transparent substrate.
In general, said substrate such as a transparent substrate can be flexible, semi-rigid or rigid.
Publicly known transparent substrate suitable for optical devices can be used as desired.
Preferably, as a transparent substrate, a transparent polymer substrate, glass substrate, thin glass substrate stacked on a transparent polymer film, transparent metal oxides (for example, oxide silicone, oxide aluminum, oxide titanium), polymer film substrate with transparent metal oxides, can be used. Even more preferably it is a transparent polymer substrate or a glass substrate.
A transparent polymer substrate can be made from polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinylchloride, polyvinyl alcohol, polyvinylvutyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-erfluoroalkylvinyl ether copolymer, polyvinyl fluoride, tetraflyoroethylene ethylene copolymer, tetrafluoroethylene hexafluoro polymer copolymer, or a combination of any of these.
The term “transparent” means at least around 60% of incident light transmittal at the thickness used in a photovoltaic device and at a wavelength or a range of wavelength used during operation of photovoltaic cells. Preferably, it is over 70%, more preferably, over 75%, the most preferably, it is over 80%.
Bank Composition
the bank (150) is obtained or obtainable from, or a cured layer of the bank composition comprises at least
Here, the term “(meth)acryloyloxy group” is a general term for the acryloyloxy group and the methacryloyloxy group. This compound is a compound that can form a crosslinked structure by reacting with the alkali-soluble polymer. Here, in order to form a crosslinked structure, a compound containing two or more acryloyloxy groups or methacryloyloxy groups, which are reactive groups, is needed, and in order to form a higher-order crosslinked structure, it preferably contains three or more acryloyloxy groups or methacryloyloxy groups.
Further, the (meth)acryloyloxy group-containing compounds can be used alone or in combination of two or more.
Preferably said chemical compound containing at least two (meth)acryloyloxy groups, is a poly acrylate monomer having at least three (meth)acryloyloxy groups, more preferably it is a poly acrylate monomer selected from one or more member of the group consisting of a poly acrylate monomer having three (meth)acryloyloxy groups, a poly acrylate monomer having four (meth)acryloyloxy groups, a poly acrylate monomer having five (meth)acryloyloxy groups, a poly acrylate monomer having six (meth)acryloyloxy groups, even more preferably it is a poly acrylate monomer having five (meth)acryloyloxy groups, a poly acrylate monomer having six (meth)acryloyloxy groups or a mixture of thereof,
Alkali-Soluble Polymer
The composition according to the present invention comprises an alkali-soluble polymer.
The alkali-soluble polymer used in the present invention preferably comprises an acryloyl group. Further, the alkali-soluble polymer used in the present invention is not particularly limited and is preferably selected from a polysiloxane containing a siloxane bond in its main skeleton, and a (meth)acrylate polymer. Among them, it is more preferable to use a methacrylate polymer, an acrylate polymer or a combination of thereof, even more preferably it is an acrylate polymer
The alkali-soluble polymer used in the present invention can have a carboxyl group. By having a carboxyl group, the solubility of the alkali-soluble polymer in a low-concentration developer can be improved.
According to the present invention, the term “Alkali-soluble polymer” means a polymer soluble in 2.38% TMAH aqueous solution at 23.0±0.1° C.
Here, the term “(meth)acrylate” is a general term for an acrylate and a methacrylate.
According to the present invention, when a low-concentration developer is used and/or low curing temperature is applied, it is preferable to use one or more of (meth)acrylate polymers.
The alkali-soluble polymer used in the present invention can be selected from generally used methacrylate polymer, an acrylate polymer or a combination of thereof, more preferably it is an acrylic polymer, for example, polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, polyalkyl methacrylate, and the like. The acrylic polymer used in the present invention preferably comprises a repeating unit containing an acryloyl group, and also preferably further comprises a repeating unit containing a carboxyl group and/or a repeating unit containing an alkoxysilyl group.
Although the repeating unit containing a carboxyl group is not particularly limited as long as it is a repeating unit containing a carboxyl group at its side chain, a repeating unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof is preferable.
Although the repeating unit containing an alkoxysilyl group can be a repeating unit containing an alkoxysilyl group at its side chain, it is preferably a repeating unit derived from a monomer represented by the following formula (B):
XB—(CH2)a—Si(ORB)b(CH3)3-b (B)
wherein,
XB is a vinyl group, a styryl group or a (meth)acryloyloxy group, RB is a methyl group or an ethyl group, a is an integer of 0 to 3, and b is an integer of 1 to 3.
Further, it is preferable that the above-described polymer contains a repeating unit containing a hydroxyl group, which is derived from a hydroxyl group-containing unsaturated monomer.
The mass average molecular weight of the alkali-soluble polymer according to the present invention is not particularly limited, and preferably it is in the range from 1,000 to 100,000, more preferably it is from 1,200 to 80,000, even more preferably 1,000 to 40,000, furthermore preferably 2,000 to 30,000. Here, the mass average molecular weight is a mass average molecular weight in terms of polystyrene according to gel permeation chromatography. In addition, as far as the number of acid groups is concerned, preferably the solid-acid value of the alkaline soluble polymer is in the range from 10 to 500 mg KOH/g, more preferably it is from 20 to 300 mg KOH/g, even more preferably from 40 to 190 mgKOH/g, furthermore preferably 60 to 150 mgKOH/g, from the viewpoint of enabling development with a low-concentration alkaline developer and achieving both reactivity and storage stability. For examples, 2-Propenoic acid, 2-methyl-, polymer with 2-hydroxyethyl 2-methyl-2-propenoate, 2-isocyanatoethyl 2-propenoate and methyl 2-methyl-2-propenoate (C6H10O3·C6H7NO3·C5H8O2. C4H6O2)x (CAS Registry Number 1615232-03-05) can be used preferably.
Polysiloxane
The alkali-soluble polymer preferably contains a siloxane (Si—O—Si) bond as its main skeleton. In the present invention, polymer containing a siloxane bond as its main skeleton is referred to as polysiloxane. Depending on the number of the oxygen atoms bonded to a silicon atom, the skeleton structure of polysiloxane can be classified as follows: a silicone skeleton (the number of oxygen atoms bonded to a silicon atom is 2), a silsesquioxane skeleton (the number of oxygen atoms bonded to a silicon atom is 3), and a silica skeleton (the number of oxygen atoms bonded to a silicon atom is 4). In the present invention, any of these can be used. The polysiloxane molecule can contain a combination of a plurality of these skeletal structures. Preferably, polysiloxane used in the present invention contains a silsesquioxane skeleton.
Polysiloxane generally has a silanol group or an alkoxysilyl group. Such silanol group and alkoxysilyl group mean a hydroxyl group and alkoxy group directly bonded to a silicon that forms a siloxane skeleton. Here, the silanol group and alkoxysilyl group are considered to contribute to the reaction with the silicon-containing compound described below, in addition to the action of accelerating the curing reaction when forming a cured film using the composition. For this reason, it is preferable that polysiloxane has these groups.
As such a (meth)acrylate polymer and/or a polysiloxane, publicly available polymer like described in WO2021/018927 A1 can be used preferably.
In some embodiments, a mixture of the polysiloxane and acrylic polymer can be used as the alkali-soluble polymer.
Further, a cured film is formed through application of the composition according to the present invention onto a substrate, image wise exposure, and development. At this time, it is necessary that a difference in solubility occurs between the exposed area and the unexposed area, and the coating film in the unexposed area should have a certain or more solubility in a developer. For example, it is considered that a pattern can be formed by exposure and development if dissolution rate of the coating film after pre-baked, in a 2.38% tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) aqueous solution (hereinafter sometimes referred to as alkali dissolution rate or ADR, which is described later in detail) is 50 Å/sec or more. However, since the required solubility varies depending on the film thickness of the cured film to be formed and the development conditions, the alkali-soluble polymer should be appropriately selected according to the development conditions. Although it varies depending on the type and addition amount of the photosensitizer or the silanol catalyst contained in the composition, for example, if the film thickness is 0.1 to 100 μm (1,000 to 1,000,000 Å), the dissolution rate in a 2.38% TMAH aqueous solution is preferably 50 to 20,000 Å/sec, and more preferably 100 to 10,000 Å/sec.
[Measurement of Alkaline Dissolution Rate (ADR) and Calculation Method Thereof]
Using a TMAH aqueous solution as an alkaline solution, the alkali dissolution rate of the alkali-soluble polymer is measured and calculated as described below.
The alkali-soluble polymer is diluted with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) so as to be 35 mass % and dissolved while stirring at room temperature with a stirrer for 1 hour. In a clean room under an atmosphere of temperature of 23.0±0.5° C. and humidity of 50±5.0%, using a pipette, 1 cc of the prepared alkali-soluble polymer solution is dropped on the center area of a 4-inch silicon wafer having a thickness of 525 μm and spin-coated to make a film having a thickness of 2±0.1 μm, and then the film is heated on a hot plate at 100° C. for 90 seconds to remove the solvent. The film thickness of the coating film is measured with a spectroscopic ellipsometer (manufactured by J.A. Woollam).
Next, the silicon wafer having this film is gently immersed in a glass petri dish having a diameter of 6 inches, into which 100 ml of a TMAH aqueous solution adjusted to 23.0±0.1° C. and having a predetermined concentration was put, then allowed to stand, and the time until the coating film disappears is measured. The dissolution rate is determined by dividing by the time until the film in the area of 10 mm inside from the wafer edge disappears.
In the case that the dissolution rate is remarkably slow, the wafer is immersed in a TMAH aqueous solution for a certain period and then heated for 5 minutes on a hot plate at 200° C. to remove moisture taken in the film during the dissolution rate measurement. Thereafter, film thickness is measured, and the dissolution rate is calculated by dividing the amount of change in film thickness before and after the immersion, by the immersion time. The above measurement method is performed 5 times, and the average of the obtained values is taken as the dissolution rate of the alkali-soluble polymer.
Polymerization Initiator
The composition according to the present invention comprises a polymerization initiator. The polymerization initiator includes a polymerization initiator that generates an acid, a base or a radical by radiation, and a polymerization initiator that generates an acid, a base or a radical by heat. In the present invention, the former is preferable and the photo radical generator is more preferable, in terms of process shortening and cost since the reaction is initiated immediately after the radiation irradiation and the reheating process performed after the radiation irradiation and before the developing process can be omitted.
The photo radical generator can improve the resolution by strengthening the pattern shape or increasing the contrast of development. The photo radical generator used in the present invention is a photo radical generator that emits a radical when irradiated with radiation. Here, examples of the radiation include visible light, ultraviolet light, infrared light, X-ray, electron beam, α-ray, and γ-ray.
The addition amount of the photo radical generator is preferably 0.001 to 50 mass %, more preferably 0.01 to 30 mass %, based on the total mass of the alkali-soluble polymer, though the optimal amount thereof depends on the type and amount of active substance generated by decomposition of the photo radical generator, the required photosensitivity, and the required dissolution contrast between the exposed area and unexposed area. If the addition amount is less than 0.001 mass %, the dissolution contrast between the exposed area and unexposed portion is too low, and the addition effect is not sometimes exhibited. On the other hand, when the addition amount of the photo radical generator is more than 50 mass %, colorless transparency of the coated film sometimes decreases, because it sometimes occurs that cracks are generated in the coated film to be formed and coloring due to decomposition of the photo radical generator becomes remarkable. Further, when the addition amount becomes large, thermal decomposition of the photo radical generator causes deterioration of the electrical insulation of the cured product and release of gas, which sometimes become a problem in subsequent processes. Further, the resistance of the coated film to a photoresist stripper containing monoethanolamine or the like as a main component sometimes deteriorates.
Examples of the photo radical generator include azo-based, peroxide-based, acylphosphine oxide-based, alkylphenone-based, oxime ester-based, and titanocene-based initiators. Among them, alkylphenone-based, acylphosphine oxide-based and oxime ester-based initiators are preferred, and 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)-phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, bis (2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(0-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like are included.
Surfactant
Further, the composition according to the present invention can optionally comprise a surfactant. Preferably it is a nonionic surfactant, preferably said nonionic surfactant is a hydrocarbon based nonionic surfactant, fluorine-based nonionic surfactant, such as Fluorad (trade name, 3M Japan Limited), Megafac (trade name, DIC Corporation), Surflon (trade name, AGC Inc.), organosilicon based nonionic surfactant, such as KP341 (trade name, Shin-Etsu Chemical Co., Ltd.) or a combination of these, more preferably said hydrocarbon based nonionic surfactant is selected from one or more members the group consisting of polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diester; polyoxyethylene fatty acid monoester; polyoxyethylene polyoxypropylene block polymer; acetylene alcohol; acetylene glycol such as 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 2,5-di-methyl-3-hexyne-2,5-diol, 2,5-di-methyl-2,5-hexanediol; polyethoxylate of acetylene alcohol; acetylene glycol derivatives, such as polyethoxylate of acetylene glycol; preferably fluorine-based nonionic surfactant is selected from one or more of fluorine-containing surfactants; preferably said hydrocarbon based nonionic surfactant is selected from organosiloxane surfactants, preferably the surfactant is a fluorine-based nonionic surfactant. Especially, Megafac RS series (trade name, DIC Corporation) is the most suitable one for the present invention from the view point of realizing improved hydrophobic bank surface, and/or realizing improved oil-repellent bank surface (especially realizing an oil-repellent surface of the top part of a bank after fabrication of it).
Preferably the total amount of the surfactant is in the range from 0.001 to 5 wt. %, more preferably from 0.01 to 4 wt. %, even more preferably from 0.05 to 3 wt. %, furthermore preferably from 0.1 to 1 wt. % based on the total amount of the total solid contents of the bank composition (bank composition).
The surfactant is added for the purpose of improving coating properties, developability, realizing improved hydrophobic bank surface, and/or realizing improved oil-repellent bank surface.
Saccharide
In a preferred embodiment of the present invention, the bank composition further comprises a saccharide, preferably the total amount of the surfactant is in the range from 0.001 to 1 wt. %, more preferably from 0.1 to 60 wt. %, even more preferably from 1 to 40 wt. %, furthermore preferably from 10 to 30 wt. % based on the total solid contents of the bank composition.
According to the study of the present inventors, it has been found that such a saccharide has a dissolution promoting effect in a developer. It is considered that saccharide is dissolved in the solvent in the composition and dissolved also in the developer, thus having a dissolution promoting effect, because it has hydrophilicity and hydrophobicity. Such an effect is particularly beneficial when the development of the composition according to the present invention is carried out with a low-concentration developer.
In a preferred embodiment of the present invention, said saccharide is selected from a monosaccharide, an oligosaccharide, a polysaccharide or a mixture of thereof, more preferably it is an oligosaccharide, even more preferably said saccharide is an oligosaccharide formed by dehydrating and condensing 2 to 10 molecules of a monosaccharide, and also includes a cyclic oligosaccharide (for example, cyclodextrin), furthermore preferably it is cyclodextrin or disaccharide obtained by condensing two molecules of monosaccharide, even more preferably it is a disaccharide obtained by condensing two molecules of monosaccharide, furthermore preferably the saccharide is oligosaccharide having an alkylene oxide having 1 to 6 carbon atoms, more preferably it has an alkylene oxide having 2 to 5 carbon atoms, and further preferably it has an ethylene oxide or propylene oxide, particularly preferably it is sucrose-alkyleneoxide-lauricacid ester.
Colorant
In a preferred embodiment of the present invention, the bank composition further comprises a colorant, preferably the total amount of said colorant is 3 to 80 wt. %, preferably 5 to 50 wt. % based on the total amount of the solid contents of the bank composition.
Preferably said colorant is an organic colorant and/or an inorganic colorant, more preferably it is a black colorant selected from an organic black pigment and/or inorganic black pigment, preferably said black colorant has a light transmittance ratio represented by [light transmittance at the wavelength of 365 nm]/[light transmittance at the wavelength of 500 nm] of 1.2 or more, more preferably the ratio is 2.0 or more, preferably said black colorant has a light transmittance ratio represented by [light transmittance at the wavelength of 365 nm]/[light transmittance at the wavelength of 500 nm] of 5.0 or less, even more preferably it is in the range from 1.2 to 5.0, further more preferably it is from 2.0 to 4.0 provided that the transmittance is obtained by measuring a film obtained by the following steps: applying a composition in which 10 mass % of a black colorant is dispersed based on the total amount of the resin forming a film having a film thickness of 10 μm by applying said composition to a glass substrate, and curing at 100° C., then the obtained film is measured using UV-vis-NIR (Hitachi High-Technologies Corporation), preferably said inorganic black pigment is zirconium nitride, preferably said organic black pigment is a mixture of two or more organic color pigments, more preferably it is a mixture of red, green blue organic color pigments configured to show black color by mixing, further more preferably said organic black pigment is a mixture selected from the group consisting of an azo type, a phthalocyanine type, a quinacridone type, a benzimidazolone type, an isoindolinone type, a dioxazine type, an indanthrene type and a perylene type organic pigments, particularly preferably said organic black pigment is a mixture of one selected from the group consisting of C. I. Pigment Orange 43, C. I. Pigment Orange 64 and C. I. Pigment Orange 72, with C. I. Pigment Blue 60, C. I. Pigment Green 7, C. I. Pigment Green 36 and C. I. Pigment Green 58.
As the colorant used in the present invention (preferably black colorant), either an inorganic pigment or an organic pigment, or a combination of two or more pigments can be used as long as it satisfies the required absorbance.
When an organic type black colorant is used in the bank, it is preferable to combine two or more organic pigments to obtain a black colorant. For examples, by mixing respective colors of red, green and blue organic pigments, a black color colorant can be obtained.
The colorant used in the present invention can be used in combination with a dispersant. As the dispersant, an organic compound-based dispersant such as a polymer dispersant described, for example, in JP-A 2004-292672 can be used.
Solvent
In a preferred embodiment of the present invention, the bank composition further comprises a solvent.
The type solvent is not particularly limited and publicly available solvents can be used as long as it can uniformly dissolve or disperse the above-described alkali-soluble polymer, the polymerization initiator and a chemical compound containing at least two (meth)acryloyloxy groups.
Preferably said solvent is selected from one or more of the 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; ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers, such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol alkyl ether acetates such as PGMEA, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; aromatic hydrocarbons, such as benzene, toluene and xylene; ketones, such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; esters, such as ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; and cyclic esters, such as γ-butyrolactone, more preferably said solvent is a combination of propylene glycol alkyl ether acetates or esters, and cyclic esters, such as γ-butyrolactone, preferably the total amount of said solvent based on the total amount of the composition is in the range from 1 wt. % to 99 wt. %, preferably from 5 wt. % to 90 wt. %, even more preferably from 10 wt. % to 80 wt. %, furthermore preferably from 20 wt. % to 70 wt. %.
Other Additives
The composition according to the present invention can optionally comprise other additives. As such additives, a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, a photosensitizing enhancing agent, a crosslinking agent, a curing agent can be added.
Thus, according to the present invention, preferably the bank composition further comprises at least one additive selected from one or more members of the group consisting of a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, a photosensitizing enhancing agent, a crosslinking agent, and/or a curing agent.
The developer dissolution accelerator or scum remover has a function of adjusting the solubility of the formed coated film in the developer and preventing scum from remaining on the substrate after development. As such an additive, crown ether can be used. The crown ether having the simplest structure is represented by the general formula (—CH2—CH2—O—)n. Preferred in the present invention are those in which n is 4 to 7. When x is set to be the total number of atoms constituting the ring and y is set to be the number of oxygen atoms contained therein, the crown ether is sometimes called x-crown-y-ethers. In the present invention, preferred is selected from the group consisting of crown ethers, wherein x=12, 15, 18 or 21, and y=x/3, and their benzo condensates and cyclohexyl condensates. Specific examples of more preferred crown ethers include 21-crown-7-ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dibenzo-21-crown-7-ether, dibenzo-18-crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether, dicyclohexyl-18-crown-6-ether, dicyclo-hexyl-15-crown-5-ether, and dicyclohexyl-12-crown-4-ether. In the present invention, among them, most preferred is selected from 18-crown-6-ether and 15-crown-5-ether. The content thereof is preferably 0.05 to 15 mass %, more preferably 0.1 to 10 mass %, based on the total mass of the alkali-soluble polymer.
The adhesion enhancer has an effect of preventing a pattern from peeling off due to stress applied after baking when a cured film is formed using the composition according to the present invention. As the adhesion enhancer, imidazoles, silane coupling agents, and the like are preferred. Among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole and 2-aminoimidazole are preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole and imidazole are particularly preferably used.
As the silane coupling agent, known ones are suitably used, and examples thereof include epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and the like. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl-triethoxysilane, N-2-(aminoethyl)-3-aminopropyltri-methoxysilane, N-2-(aminoethyl)-3-aminopropyltri-ethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino-propyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like are preferred. These can be used alone or in combination of two or more, and the addition amount thereof is preferably 0.05 to 15 mass % based on the total mass of the alkali-soluble polymer.
Further, as the silane coupling agent, a silane compound and siloxane compound having an acid group, or the like can be used. Examples of the acid group include a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, and the like. When it contains a monobasic acid group such as a carboxyl group or a phenolic hydroxyl group, it is preferred that a single silicon-containing compound has a plurality of acid groups.
Exemplified embodiments of such a silane coupling agent include a compound represented by the formula (C):
XnSi(ORC3)4-n (C)
or polymer obtained using it as a repeating unit. At this time, a plurality of repeating units having different X or RC3 can be used in combination.
In the formula, RC3 includes a hydrocarbon group, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. In the general formula (C), a plurality of RC3 are included, and each RC3 can be identical or different.
As X, those having an acid group such as phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfo, and alcohol group are included, and those in which these acid groups are protected by acetyl, aryl, amyl, benzyl, methoxymethyl, mesyl, tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl or trityl group, and an acid anhydride group are included.
Among them, a compound having a methyl group as RC3 and a carboxylic acid anhydride group as X, such as an acid anhydride group-containing silicone, is preferable. More specifically, a compound represented by the following formula (X-12-967C (trade name, Shin-Etsu Chemical Co., Ltd.)) or polymer containing a structure corresponding thereto in its terminal or side chain of a silicon-containing polymer such as silicone is preferred.
Further, a compound in which thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, and an acid group such as sulfo group is provided at the terminal of dimethyl silicone is also preferable. As such a compound, compounds represented by the following formulae (X-22-2290AS and X-22-1821 (trade name in every case, Shin-Etsu Chemical Co., Ltd.)) are included.
When the silane coupling agent has a silicone structure, if the molecular weight is too large, the compatibility with polysiloxane contained in the composition becomes poor, so that there is a possibility that there is an adverse effect such that the solubility in the developer does not improve, the reactive group remains in the film, and the chemical resistance that can withstand the subsequent process cannot be maintained. For this reason, the mass average molecular weight of the silane coupling agent is preferably 5,000 or less, and more preferably 4,000 or less. The content of the silane coupling agent is preferably 0.01 to 15 mass % based on the total mass of the alkali-soluble polymer.
As the polymerization inhibitor, an ultraviolet absorber as well as nitrone, nitroxide radical, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amine and derivatives thereof can be added. Among them, methylhydroquinone, catechol, 4-t-butylcatechol, 3-methoxycatechol, phenothiazine, chlorpromazine, phenoxazine, TINUVIN 144, 292 and 5100 (BASF) as the hindered amine, and TINUVIN 326, 328, 384-2, 400 and 477 (BASF) as the ultraviolet absorber are preferred. These can be used alone or in combination of two or more, and the content thereof is preferably 0.01 to 20 mass % based on the total mass of the alkali-soluble polymer.
As the antifoaming agent, alcohols (C1-18), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethers such as polyethylene glycols (PEG) (Mn: 200 to 10,000) and polypropylene glycols (PPG) (Mn: 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil and fluoro-silicone oil, and organo-siloxane-based surfactants described in detail below are included. These can be used alone or in combination of a plurality of these, and the content thereof is preferably 0.1 to 3 mass % based on the total mass of the alkali-soluble polymer.
Photosensitizing Enhancing Agent
A photosensitizing enhancing agent can be optionally added to the bank composition according to the present invention. The photosensitizing enhancing agent preferably used in the composition according to the present invention includes coumarin, ketocoumarin and their derivatives, thiopyrylium salts, acetophenones, and the like, and specifically, p-bis(o-methylstyryl) benzene, 7-dimethylamino-4-methylquinolone-2,7-amino-4-methylcoumarin, 4,6-di-methyl-7-ethylaminocoumarin, 2-(p-dimethylamino-styryl)-pyridylmethyl-iodide, 7-diethylaminocoumarin, 7-diethylamino-4-methyl-coumarin, 2,3,5,6-1H,4H-tetrahydro-8-methyl-quinolizino-<9,9a,1-gh>coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethyl-amino-4-trifluoro-methylcoumarin, 7-amino-4-trifluoro-methylcoumarin, 2,3,5,6-1H,4H-tetrahydroquinolizino-<9,9a,1-gh>coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoro-methylcoumarin, 2,3,5,6-1H,4H-tetrahydro-9-carbo-ethoxyquinolizino-<9,9a,1-gh>coumarin, 3-(2′-N-methylbenzimidazolyl)-7-N,N-diethylaminocoumarin, N-methyl-4-trifluoro-methylpiperidino-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolylethyl iodide, 3-(2′-benzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2′-benzothiazolyl)-7-N,N-diethylaminocoumarin, and sensitizing dyes such as pyrylium salts and thiopyrylium salts represented by the following chemical formula. By the addition of the sensitizing dye, patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 nm) becomes possible. The content thereof is preferably 0.05 to 15 mass %, more preferably 0.1 to 10 mass %, based on the total mass of the alkali-soluble polymer.
Further, as the photosensitizing enhancing agent, an anthracene skeleton-containing compound can be also used. Specifically, a compound represented by the following formula is included.
wherein, R31 each independently represents a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a halogenated alkyl group,
R32 each independently represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, and a carboalkoxy group, and
k is each independently selected from 0 and an integer of 1 to 4.
When such a photosensitizing enhancing agent having an anthracene skeleton is used, its content is preferably 0.01 to 5 mass % based on the total mass of the alkali-soluble polymer.
Optical Device
In another aspect, the invention further relates to an optical device (300, 400, 500) containing at least one color conversion device (100) and a functional medium (320, 420, 520) configured to modulate a light or configured to emit light.
In some embodiments of the present invention, the optical device can be a liquid crystal display device (LCD), Organic Light Emitting Diode (OLED), backlight unit for an optical display, Light Emitting Diode device (LED), Micro Electro Mechanical Systems (here in after “MEMS”), electro wetting display, or an electrophoretic display, a lighting device, and/or a solar cell.
The term “emission” means the emission of electromagnetic waves by electron transitions in atoms and molecules.
Process
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;
Preferably said composition comprises a (meth)acrylate monomer represented by following chemical formula (II) as detailly described in the section of “The composition and (meth)acrylate monomer” above;
And said process comprises a following step before step Y1)
In a preferable embodiment of the present invention, the method comprises a purification step of the (meth)acrylate monomers. More preferably, said purification step is taken place before step Y1) and/or Y0).
More details of details of the composition such as (meth)acrylate monomers, mixing ratio of the (meth)acrylate monomers, another material, polymer and scattering particles are described in the section of “(meth)acrylate monomer”, “polymer” and “scattering particle”.
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;
Like described in WO2021/018927 A1, known bank fabrication conditions can be used.
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.
Z—Y (XA)
wherein
where “*” represents the connecting point to symbol Y of the formula, Rx1 is a 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 phosphonate group, thiol group, a carboxyl group or a combination of any of these, more preferably it is a carboxyl group; and
Present invention provides one or more of the following effects:
Preventing/reducing long term viscosity increase of ink composition, Achieving higher cross-linking density, realizing good compatibility of (meth)acrylate monomers, selecting publically available (meth)acrylate monomers, realizing lower vaper pressure and higher boiling point, achieving a solid film with high polymerization efficiency by QD containing acrylate ink realising an improved solidity of the film derived by (meth)acrylate monomers under short time and week UV curing condition,
The working examples 1-6 below provide descriptions of the present invention, as well as an in-detail description of their fabrication.
1,6-Hexanediol dimethacrylate (HDDMA) and lauryl acrylate (LA) are stored over molecular sieves 4A. HDDMA is purified by passed through silica gel column prior to use. 4 g of HDDMA and 6 g of LA are mixed in glass vial, thus obtained a monomer mixture. The weight ratio of HDDMA:LA in the monomer mixture is 40:60.
In a same manner as described above, the monomer mixtures of HDDMA:LA (30:70), HDDMA:LA (20:80), NDDA:LA (30:70) are prepared instead of HDDMA:LA (40:60).
10.41 ml of green Cd-free InP based QD solution in toluene (Merck) and 1.02 g of the monomer mixture obtained in working example 1 are mixed in glass flask. Toluene is evaporated under vacuum at 40 deg.C by rotary evaporator, thus obtained 3.06 g of QD monomer dispersion.
The QD monomer dispersion obtained in reference example 2, the TiO2 monomer dispersion obtained in working example 3, 1.12 g of the monomer mixture obtained in working example 1, 0.051 g of photo initiator (Omnirad 819) and 0.041 g of antioxidant (Irganox 1010) are mixed in glass vial. The obtained mixture is agitated by applying ultrasonic and then by magnetic stirring to afford 5 g of the QD ink.
The QD inks obtained in reference example 3 is injected into a text cell with 15 mm gap and photo-cured by irradiating UV light.
EQE measurement is carried out by using integrating sphere equipped with excitation light by optical fiber (CWL: 450 nm) and spectrometer (C9920, Hamamatsu photonics). 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]
Wavelength Range for Calculation
Emission: [Green] 480 nm-600 nm, [Red] 560 nm-680 nm
Table 1 shows the EQE measurement results of the QD ink compositions obtained in reference example 3.
The EQE value of the 00 ink composition obtained in the comparative example is 22.7.
The QD ink composition is prepared in the same manner as described above with using the following materials.
The bank composition is prepared with using the following materials.
Saccharide A: Sucrose Ethylene Oxide Adduct
Acryl polymer B: 2-Propenoic acid, 2-methyl-, polymer with 2-hydroxyethyl 2-methyl-2-propenoate, 2-isocyanatoethyl 2-propenoate and methyl 2-methyl-2-propenoate (Natoco).
Acryl polymer A: acrylic randam polymer made from carbon acid monomer and monomer containing at least one aromatic ring group (Shin-Nakajima).
The obtained bank composition is applied onto a bared glass substrate by spin coating, then the coated glass substrate is prebaked on a hot plate at 100° C. for 90 seconds so as to prepare an average film thickness of 13 μm.
Exposure is performed using an i-line exposure machine, and cure baking is performed at 230° C. for 30 min. Then, a development is performed using 0.03% KOH for 60 seconds, and rinsing with deionaized pure water is performed for 30 seconds. As a result, a 12 μm bank (C/H) pattern is formed. Finally, sample 1 is obtained.
Then sample 2 is fabricated in the same manner as described above “fabrication of sample 1” except for 100° C. for 30 minutes cure baking condition is applied instead of 230° C. for 30 minutes cure baking condition.
Then sample 2 is obtained.
OD Calculation
The transmittance at the wavelength of 400 to 700 nm of sample 1 and sample 2 are measured with using a Spectrophotometer CM-5 (Konica Minolta, Inc.), and it is converted into the OD.
SEM Analysis
Cross Section SEM analysis of the sample 2 is performed.
FT: 11.5 μm, Taper angle: 98 deg. are observed.
According to the Cross Section SEM analysis, the well-defined pixel structure is observed. It also proves that a low curing temperature (e.g. 100° C.) properties of the bank is very good. Further, the bank composition is well developed even with a low-concentration alkaline developer
The process conditions and the obtained OD calculation results are shown in Table 3. It is also confirmed by SEM analysis that the patterns of sample 1 and 2 are formed (OK) without any peeling.
QD Ink Filing Test
Then, the QD ink obtained in working example 14 is injected into the samples 1 and 2 with 12 mm gap and photo-cured by irradiating UV light. The obtained samples 1 and 2 are very clear.
According to the cross section SEM analysis, a smooth layer structure without any void in a cured ink and without any aggregation in the cured ink is observed.
And the compatibility between the bank and the cured ink, and the wetting properties and chemical stability towards the QD ink are both very good.
According to the SEM analysis, no dissolution, no delamination of the bank structure by the QD ink, no intermixing of the bank and the QD ink are also observed.
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.
0.670 g of TiO2 stock in LA obtained in Working Example 1, 0.709 g of LA, 0.135 g of TMPTA, 8.93 g of green QD in n-octane (S-BG051, Shoei) and 0.054 g of OA are mixed in a glass flask. The mixture is stirred at 40 deg.C for 2 hours under N2 atmosphere, and then n-octane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg.C. To this mixture 0.027 g of Omnirad819 and 0.013 g of Irganox1010 are added and the mixture is stirred at room temp. until the ink becomes homogeneous, thus obtained the green QD ink of the composition (Sample A-1(OA:2 wt %)) shown in the table below.
Sample A-2 (OA: 4 wt %) is prepared in the same manner as described above expect for that 4 wt % of Oleic acid (OA) based on the total amount of the composition is used.
Sample A-3 (OA:0.5 wt %) is prepared in the same manner as described above expect for that 0.5 wt % of Oleic acid (OA) based on the total amount of the composition is used.
0.525 g of TiO2 stock in LA obtained in Working Example 1, 0.593 g of LA, 0.110 g of TMPTA and 7.00 g of green QD in n-octane (SBG051, Shoei) 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 0.021 g of Omnirad819 and 0.011 g of Irganox1010 are added and the mixture is stirred at room temp. until the ink becomes homogeneous, thus obtained the green QD ink of the composition (Sample B).
6.0 g of Red QD in heptane (SRF180921-01-RED-02, Nanosys) is put in a glass flask and heptane is evaporated by rotary evaporator under vacuum at 40 deg.C. The dried QD is dissolved in 12.6 ml of anhydrous THE and to the solution 0.4 ml of OA is added. The mixture is heated to reflux under N2 atmosphere for 2 hours, and after cooling down the solution the red QD was precipitated out by adding 60 ml of dry acetone. Then the turbid solution is centrifuged at 6,000G 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 Working Example 1, 1.274 g of LA, 0.491 g of HDDA, 3.500 g of red QD in n-octane obtained in working example 3 (LE) 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 (Sample C) shown in the table below.
1.119 g of TiO2 stock in LA obtained in example 1, 1.264 g of LA, 0.906 g of HDDMA, 3.000 g of red QD in heptane (SRF180921-01-RED-02, Nanosys) are mixed in a glass flask and heptane in the mixture is evaporated by rotary evaporator under vacuum at 40 deg.C. To this mixture 0.045 g of Omnirad819 and 0.022 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 (Sample D) shown in the table below.
Viscosity trends of samples A1 to A3 and sample B are measured with using a viscometer (Viscomate VM-10A, Sekonic) at 25 deg.C in air.
Sample A-1 from Working Example 2 and Sample E as a comparative example are used for Wiping Test. Following table shows the test results.
UV curing condition: 100 mW/cm2 with 395 nm UV LED under nitrogen flow (O2 concentration: 0.1%)
Sample E (comparative example):
| Number | Date | Country | Kind |
|---|---|---|---|
| 20202992.2 | Oct 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/078730 | 10/18/2021 | WO |
