WO2018016589A1 - 量子ドット含有組成物、波長変換部材、バックライトユニット、および液晶表示装置 - Google Patents
量子ドット含有組成物、波長変換部材、バックライトユニット、および液晶表示装置 Download PDFInfo
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Definitions
- the present disclosure relates to a quantum dot-containing composition, a wavelength conversion member, a backlight unit, and a liquid crystal display device.
- liquid crystal display devices Liquid Crystal Display (also abbreviated as LCD for short)
- LCD liquid Crystal Display
- the liquid crystal display device is composed of at least a backlight and a liquid crystal cell, and usually further includes members such as a backlight side polarizing plate and a viewing side polarizing plate.
- the wavelength conversion member of the backlight unit is provided with a wavelength conversion layer containing a quantum dot (also called Quantum Dot, QD, or quantum dot) as a light emitting material.
- a quantum dot also called Quantum Dot, QD, or quantum dot
- the wavelength conversion member is a member that converts the wavelength of light incident from the light source and emits it as white light.
- the wavelength conversion layer that includes quantum dots as the light emitting material the light emission characteristics excited by the light incident from the light source White light can be generated using fluorescence emitted by two or three different quantum dots.
- Fluorescence due to quantum dots has high brightness and a small half-value width, so that LCDs using quantum dots are excellent in color reproducibility.
- the color gamut has been expanded from 72% to 100% NTSC (National Television System Committee) ratio.
- a ligand is coordinated on the surface of the quantum dot for the purpose of improving the affinity between the solvent and the quantum dot in the composition or improving the luminous efficiency.
- a ligand may be contained in the composition containing quantum dots.
- JP 2012-525467 A discloses a composition containing quantum dots and a polymer ligand.
- the polymeric ligand has a silicone backbone and one or more amino groups and amino moieties linked to the silicone backbone.
- Japanese Patent Application Laid-Open No. 2011-514879 discloses nanoparticles having a ligand bonded to the surface.
- This ligand is represented by the formula X-Sp-Z, where X is selected from a primary amine group, a secondary amine group, urea, and the like, and Sp is a spacer group capable of charge transfer, Z is a reactive group that imparts specific chemical reactivity to the nanoparticles.
- reactive groups thiol groups, carboxyl groups and the like are described.
- the wavelength conversion member used in the display device is required to have a high level of characteristics and long-term reliability.
- the luminous efficiency of the quantum dots gradually decreases due to storage in a high-temperature environment or a rise in the temperature of the main body due to use, and luminance decreases accordingly. There was a problem.
- a wavelength conversion member using quantum dots is generally provided as a wavelength conversion film including a wavelength conversion layer containing quantum dots, and is incorporated in a backlight unit of a liquid crystal display device.
- liquid crystal display devices such as smartphone display devices have become thinner, and the wavelength conversion film is also desired to be thinner.
- the binder resin of the wavelength conversion layer is preferably an acrylate resin with excellent productivity, but it has been difficult to disperse the quantum dots in a high concentration in the acrylate resin, and the wavelength conversion layer cannot be thinned.
- the present disclosure provides a quantum dot-containing composition that can suppress a decrease in luminance due to heat, disperse the quantum dots in a high concentration in the acrylate resin, and thin the wavelength conversion layer. To do.
- the present disclosure provides a wavelength conversion member, a backlight unit, and a liquid crystal display device that are capable of being reduced in thickness because luminance reduction due to heat is suppressed.
- the present inventors speculated that the decrease in luminance of the quantum dots due to heat was caused by the fact that the ligand covering the surface of the quantum dots was detached from the surface of the quantum dots due to heat.
- the ligand deviates from the surface of the quantum dot, a surface level is generated in that portion, and exciton is trapped there, so that the luminous efficiency is lowered.
- the surface of the quantum dot is easily oxidized by oxygen present in the external environment, resulting in deterioration of the quantum dot.
- the removal of the ligand promotes the aggregation of the quantum dots, leading to a decrease in luminous efficiency.
- the ligand also has an effect of imparting dispersion stability to the binder resin to the quantum dots. Therefore, the ligand that can effectively cover the surface of the quantum dots increases the dispersion stability of the quantum dots with respect to the acrylate resin, and enables the concentration of the quantum dots to be increased. Based on such knowledge, the present disclosure provides various aspects described below.
- the quantum dot-containing composition of the present disclosure includes a quantum dot and a ligand having a coordinating group that coordinates to the surface of the quantum dot, and the ligand is represented by the following general formula I.
- A is an organic group containing one or more coordinating groups selected from an amino group, a carboxy group, a mercapto group, a phosphine group, and a phosphine oxide group, and Z is an (n + m + l) -valent organic group.
- a linking group, R is an optionally substituted alkyl group, alkenyl group or alkynyl group, Y is a polymerization degree of 3 or more, polyacrylate skeleton, polymethacrylate skeleton, This is a group having a polymer chain containing at least one skeleton selected from a polyacrylamide skeleton, a polymethacrylamide skeleton, a polyester skeleton, a polyurethane skeleton, a polyurea skeleton, a polyamide skeleton, a polyether skeleton, and a polystyrene skeleton.
- n and m are each independently a number of 1 or more, l is a number of 0 or more, and n + m + 1 is an integer of 3 or more.
- the n A's may be the same or different.
- the m Ys may be the same or different.
- 1 R may be the same or different. However, at least two coordinating groups are contained in the molecule.
- the ligand is preferably one represented by the following general formula II.
- L is a coordinating group
- X 1 is an (a + 1) -valent organic linking group
- S is a sulfur atom.
- a L may be the same or different.
- a is an integer of 1 or more and 2 or less. When a is 1, n is 2 or more, and when a is 2, n is 1 or more.
- the ligand is preferably one represented by the following general formula III.
- X 2 and X 3 are divalent organic linking groups
- P has a degree of polymerization of 3 or more, and is a polyacrylate skeleton, polymethacrylate skeleton, polyacrylamide skeleton, polymethacrylamide skeleton
- the polymer chain includes at least one skeleton selected from a polyester skeleton, a polyurethane skeleton, a polyurea skeleton, a polyamide skeleton, a polyether skeleton, and a polystyrene skeleton.
- Q is an alkyl group, alkenyl group or alkynyl group which may have a substituent.
- the quantum dot-containing composition of the present disclosure may further include a polymerizable compound.
- the quantum dot-containing composition of the present disclosure may further include at least one polymer and at least one solvent.
- the polymer may be a water soluble polymer.
- the water-soluble polymer may be polyvinyl alcohol or an ethylene-vinyl alcohol copolymer.
- the quantum dots are quantum dots having an emission center wavelength in a wavelength band of 600 nm to 680 nm, quantum dots having an emission center wavelength in a wavelength band of 520 nm to 560 nm, and quantum dots having an emission center wavelength in a wavelength band of 430 nm to 480 nm. It is preferable that it is at least one selected.
- the wavelength conversion member of the present disclosure has a wavelength conversion layer formed by curing the quantum dot-containing composition of the present disclosure. That is, the wavelength conversion layer includes a cured product of the quantum dot-containing composition of the present disclosure.
- the wavelength conversion member of the present disclosure has a barrier film having an oxygen permeability of 1.00 cm 3 / m 2 ⁇ day ⁇ atm or less, and at least one of the two main surfaces of the wavelength conversion layer is a barrier film. It is preferable to contact.
- the wavelength conversion member of the present disclosure has two barrier films, and the two main surfaces of the wavelength conversion layer are respectively in contact with the barrier film.
- the wavelength conversion layer preferably has a thickness of 30 ⁇ m or less.
- the barrier film preferably has a thickness of 30 ⁇ m or less per sheet. The above range is preferable because the wavelength conversion member can be incorporated into a small liquid crystal display device such as a smartphone.
- the backlight unit of the present disclosure includes at least the wavelength conversion member and the light source of the present disclosure.
- the liquid crystal display device of the present disclosure includes at least the backlight unit and the liquid crystal cell of the present disclosure.
- the quantum dot-containing composition of the present disclosure includes a quantum dot and a ligand having a coordinating group coordinated on the surface of the quantum dot, and the ligand is represented by the above general formula I. . Since the ligand in the quantum dot composition of the present disclosure has the above-described structure, the coordinating group is coordinated multipointly in a narrow region of the quantum dot. Therefore, the ligand can be prevented from being detached from the surface of the quantum dot by heat, and the luminance can be prevented from being lowered. Further, since the quantum dots can be contained at a high concentration, the wavelength conversion layer can be thinned. A wavelength conversion member, a backlight, and a liquid crystal display device provided with a wavelength conversion layer obtained by curing such a quantum dot-containing composition are satisfactorily suppressed in luminance reduction due to heat, and can be made thinner.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the “half-value width” of a peak means a peak width at a height of peak height ⁇ 1 ⁇ 2.
- the light having the emission center wavelength in the wavelength band of 430 to 480 nm is called blue light
- the light having the emission center wavelength in the wavelength band of 520 to 560 nm is called green light
- the emission center wavelength in the wavelength band of 600 to 680 nm The light having a color is called red light.
- the (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group.
- Quantum dot-containing composition [Quantum dot-containing composition] Hereinafter, details of the quantum dot-containing composition will be described.
- Quantum dots are semiconductor nanoparticles that emit fluorescence when excited by excitation light.
- the quantum dot-containing composition may contain two or more types of quantum dots having different emission characteristics as quantum dots.
- the quantum dot-containing composition is excited by being excited by the blue light L B fluorescent quantum dots emits (red light) L R, and the blue light L B fluorescence It may contain quantum dots that emit (green light) L G.
- the quantum dot-containing composition is excited by ultraviolet light L UV to emit fluorescence (red light) LR, and is excited and excited by ultraviolet light L UV. it can be excited by the quantum dots, and the ultraviolet light L UV emits (green light) L G and containing quantum dots to emit fluorescence (blue light) L B.
- the quantum dots that emit red light L R may be mentioned those having an emission center wavelength in a wavelength range of 600 ⁇ 680 nm.
- the quantum dot emits green light L G it may be mentioned those having an emission center wavelength in a wavelength range of 520 ⁇ 560 nm.
- the quantum dot emitting blue light L B may include those having an emission center wavelength in a wavelength range of 430 ⁇ 480 nm. It is preferable that a quantum dot containing composition contains at least 1 type among these as a quantum dot.
- quantum dots for example, paragraphs 0060 to 0066 of JP2012-169271A can be referred to, but the quantum dots are not limited to those described in this publication.
- quantum dots for example, core-shell type semiconductor nanoparticles are preferable from the viewpoint of improving durability.
- the core II-VI semiconductor nanoparticles, III-V semiconductor nanoparticles, multi-component semiconductor nanoparticles, and the like can be used. Specific examples include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, InP, InAs, and InGaP, but are not limited thereto. Among these, CdSe, CdTe, InP, and InGaP are preferable from the viewpoint of emitting visible light with high efficiency.
- the shell CdS, ZnS, ZnO, GaAs, and a composite thereof can be used, but the shell is not limited thereto.
- the emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles.
- the quantum dots may be spherical particles, may be rod-like particles called quantum rods, and may be tetrapod-type particles. From the viewpoint of narrowing the light emission half width (FWHM) and expanding the color reproduction range of the liquid crystal display device, spherical quantum dots or rod-like quantum dots (that is, quantum rods) are preferable.
- a ligand having a Lewis basic coordinating group may be coordinated on the surface of the quantum dot.
- Lewis basic coordinating groups include amino groups, carboxy groups, mercapto groups, phosphine groups, and phosphine oxide groups.
- hexylamine, decylamine, hexadecylamine, octadecylamine, oleylamine, myristylamine, laurylamine, oleic acid, mercaptopropionic acid, trioctylphosphine, and trioctylphosphine oxide examples include hexylamine, decylamine, hexadecylamine, octadecylamine, oleylamine, myristylamine, laurylamine, oleic acid, mercaptopropionic acid, trioctylphosphine, and trioctylphosphine oxide.
- hexadecylamine, trioctylphosphine, and trioctylphosphine oxide are preferable, and trioctylphosphine oxide is particularly preferable.
- Quantum dots coordinated with these ligands can be produced by a known synthesis method. For example, C.I. B. Murray, D.M. J. et al. Norris, M.M. G. It can be synthesized by a method described in Bawendi, Journal American Chemical Society, 1993, 115 (19), pp 8706-8715, or The Journal Physical Chemistry, 101, pp 9463-9475, 1997.
- the quantum dot which the ligand coordinated can use a commercially available thing without a restriction
- the content of the quantum dot coordinated with the ligand is preferably 0.01 to 10% by mass with respect to the total mass of the polymerizable compound contained in the quantum dot-containing composition, 0.05 to 5% by mass is more preferable.
- Quantum dots according to the present disclosure may be added to the quantum dot-containing composition in the form of particles, or may be added in the form of a dispersion dispersed in a solvent.
- the addition in the state of a dispersion is preferable from the viewpoint of suppressing the aggregation of the quantum dot particles.
- the solvent used here is not particularly limited. For example, organic solvents, such as toluene, are mentioned.
- the quantum dot-containing composition of the present disclosure includes a quantum dot and a ligand having a coordinating group coordinated on the surface of the quantum dot, and the ligand is represented by the following general formula I: .
- A is an organic group containing one or more coordinating groups selected from an amino group, a carboxy group, a mercapto group, a phosphine group, and a phosphine oxide group, and Z is an (n + m + l) -valent organic linking group.
- R is an optionally substituted alkyl group, alkenyl group or alkynyl group
- Y is a polymerization degree of 3 or more
- a polyacrylate skeleton, polymethacrylate skeleton, polyacrylamide This is a group having a polymer chain containing at least one skeleton selected from a skeleton, a polymethacrylamide skeleton, a polyester skeleton, a polyurethane skeleton, a polyurea skeleton, a polyamide skeleton, a polyether skeleton, and a polystyrene skeleton.
- n and m are each independently a number of 1 or more, l is a number of 0 or more, and n + m + 1 is an integer of 3 or more.
- the n A's may be the same or different.
- the m Ys may be the same or different.
- 1 R may be the same or different. However, at least two coordinating groups are contained in the molecule.
- Z is an (n + m + 1) -valent organic linking group.
- n + m + 1 is an integer of 3 or more, preferably 3 or more and 10 or less, more preferably 2 or more and 8 or less, and still more preferably 3 or more and 6 or less.
- n and m are each independently preferably 1 or more, n is more preferably 2 or more and 5 or less, and m is more preferably 1 or more and 5 or less.
- l is 0 or more, and preferably 0 or more and 3 or less.
- n: m is preferably in the range of 1: 4 to 4: 1
- (m + n): l is preferably in the range of 3: 2 to 5: 0.
- the (n + m + 1) -valent organic linking group represented by Z includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.
- the (n + m + 1) -valent organic linking group Z includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, and 1 to 120 hydrogen atoms. And groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 More preferred are groups consisting of up to 0 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms. Particularly preferred are groups consisting of atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.
- (n + m + l) -valent organic linking group Z include a group formed by combining the following structural units or structural units (which may form a ring structure).
- examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number of 6 such as a phenyl group and a naphthyl group. From 1 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and the like, acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups and the like.
- Alkoxy groups up to 6 halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate esters such as cyano group and t-butyl carbonate Group, and the like.
- organic linking groups (1) to (22) are shown below.
- the organic linking group Z is not limited thereto. * In the following organic linking group represents a site bonded to the A, Y, and R sides in the general formula I.
- the most preferable (n + m + 1) -valent organic linking group Z is the following group.
- R is a group containing an alkyl group, alkenyl group or alkynyl group which may have a substituent.
- the group represented by R preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.
- the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfone.
- C1-C6 acyloxy groups such as amide group, N-sulfonylamide group, acetoxy group, etc.
- C1-C6 alkoxy groups such as methoxy group, ethoxy group, halogen atoms such as chlorine and bromine, methoxycarbonyl Groups, alkoxycarbonyl groups having 2 to 7 carbon atoms such as ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, and the like.
- Y has a degree of polymerization of 3 or more, and a polyacrylate skeleton, polymethacrylate skeleton, polyacrylamide skeleton, polymethacrylamide skeleton, polyester skeleton, polyurethane skeleton, polyurea skeleton, polyamide skeleton, polyether skeleton, And a group having a polymer chain containing at least one skeleton selected from polystyrene skeletons.
- the m Ys may be the same or different.
- the polymer chain in the present disclosure is at least one selected from a polyacrylate skeleton, a polymethacrylate skeleton, a polyacrylamide skeleton, a polymethacrylamide skeleton, a polyester skeleton, a polyurethane skeleton, a polyurea skeleton, a polyamide skeleton, a polyether skeleton, and a polystyrene skeleton. It may be a polymer, a modified product, or a copolymer comprising the skeleton. Examples of the polymer chain include a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, and the like.
- the polymer chain may be any of a random copolymer, a block copolymer, and a graft copolymer. Among these, a polymer or copolymer having a polyacrylate skeleton is particularly preferable.
- the polymer chain is preferably soluble in the solvent.
- the affinity with the solvent is low, for example, when used as a ligand, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer sufficient for dispersion stabilization.
- the polymer chain preferably has a structure that allows it to be well dispersed in the polymerizable compound in the composition.
- Such polymer chains are preferably highly branched and have steric repulsion groups with each other. With such a structure, the polymerizable compound enters between the highly branched chains, and the quantum dots can be well dispersed in the polymerizable compound.
- the SP value of the polymer chain is preferably 17 to 22 MPa 1/2 .
- the monomer that forms the polymer chain is not particularly limited.
- (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, monomers having an acidic group, and the like are preferable.
- acrylic acid esters crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters
- (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, monomers having an acidic group, and the like are preferable.
- preferable examples of these monomers will be described.
- Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-Methylhexyl acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth
- Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
- Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
- Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
- Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
- Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Le acrylamide, N- hydroxy
- styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl
- acidsic substance for example, t-Boc and the like
- vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
- Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
- Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
- Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
- (meth) acrylonitrile heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. it can.
- vinyl groups eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.
- N-vinylformamide N-vinylacetamide
- N-vinylimidazole N-vinylimidazole
- vinylcaprolactone etc. it can.
- the ligand is preferably represented by the following general formula II.
- L is a coordinating group
- X 1 is an (a + 1) -valent organic linking group
- S is a sulfur atom.
- a L may be the same or different.
- a is an integer of 1 or more and 2 or less. When a is 1, n is 2 or more, and when a is 2, n is 1 or more.
- the meanings of symbols other than these in general formula II are the same as in general formula I.
- organic linking group Z When the ligand is represented by the general formula II or the following general formula III, specific examples of the (n + m + 1) -valent organic linking group Z include the above organic linking groups (1) to (22).
- the linking groups (21) and (22) are particularly preferred.
- the organic linking group Z is not limited thereto. * In the following organic linking group represents a site bonded to S (sulfur atom) in General Formula II and General Formula III.
- the ligand may be represented by the following general formula III.
- X 2 and X 3 are divalent organic linking groups
- P has a degree of polymerization of 3 or more, and is a polyacrylate skeleton, polymethacrylate skeleton, polyacrylamide skeleton, polymethacrylamide skeleton, polyester skeleton , A polymer chain containing at least one skeleton selected from a polyurethane skeleton, a polyurea skeleton, a polyamide skeleton, a polyether skeleton, and a polystyrene skeleton.
- Q is an alkyl group, alkenyl group or alkynyl group which may have a substituent. The meanings of symbols other than these in general formula III are the same as in general formula II.
- X 2 and X 3 represent a divalent organic linking group.
- the divalent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included, which may be unsubstituted or substituted.
- the divalent organic linking groups X 2 and X 3 may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to A divalent organic linking group consisting of up to 100 hydrogen atoms and 0 to 10 sulfur atoms is preferred. Single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 A divalent organic linking group consisting of up to sulfur atoms is more preferred. Single bond, or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 Particularly preferred are divalent organic linking groups consisting of up to sulfur atoms.
- examples of the substituent include carbon having 1 to 20 carbon atoms such as methyl and ethyl, carbon such as phenyl and naphthyl. Carbon number such as aryloxy group having 6 to 16 carbon atoms, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like, acyloxy group having 1 to 6 carbon atoms, methoxy group, ethoxy group, etc.
- divalent organic linking groups X 2 and X 3 include a group composed of a combination of the following structural units (which may form a ring structure).
- (A + 1) -valent organic linking group X 1 includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, and 1 to 120 hydrogen atoms.
- Preferred is a group consisting of atoms and 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to More preferred are groups consisting of up to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms.
- Particularly preferred are groups consisting of oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.
- substituents include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc. having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc.
- alkoxy groups such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, carbonic acid such as t-butyl carbonate, etc.
- An ester group and the like.
- Such A has a length of X 1 smaller than about 1 nm and has a plurality of coordinating groups in the range of this length. For this reason, since a ligand can adsorb
- the ligand in the quantum dot-containing composition of the present disclosure can be synthesized by a known synthesis method. For example, it can be synthesized by the method described in JP-A-2007-277514.
- the quantum dot-containing composition of the present disclosure may include a polymerizable compound.
- the polymerizable compound is preferably an acrylic compound.
- the polymerizable compound is preferably a monofunctional or polyfunctional (meth) acrylate monomer, and may be a monomer prepolymer or polymer as long as it has polymerizability.
- (meth) acrylate means one or both of acrylate and methacrylate.
- Monofunctional (meth) acrylate monomers include acrylic acid and methacrylic acid, derivatives thereof, and more specifically, monomers having one polymerizable unsaturated bond ((meth) acryloyl group) of (meth) acrylic acid in the molecule. Can be mentioned.
- alkyl (meth) acrylates having an alkyl group having 1 to 30 carbon atoms such as acrylate and stearyl (meth) acrylate.
- bifunctional (meth) acrylate monomer examples include neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and dipropylene glycol di (meth) acrylate.
- Trifunctional (meth) acrylate monomers can include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, and PO-modified glycerol tri (meth) acrylate.
- the (meth) acrylate monomer is preferably an alicyclic acrylate.
- monofunctional (meth) acrylate monomers include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
- bifunctional (meth) acrylate monomer include tricyclodecane dimethanol di (meth) acrylate.
- the total amount of the polymerizable compound in the quantum dot-containing composition is preferably 70 to 99 parts by mass with respect to 100 parts by mass of the quantum dot-containing composition from the viewpoint of handling and curability of the composition, 85 More preferably, it is -97 parts by mass.
- the quantum dot-containing composition may contain a known radical photopolymerization initiator or cationic polymerization initiator as a polymerization initiator.
- a known radical photopolymerization initiator or cationic polymerization initiator as a polymerization initiator.
- the photopolymerization initiator for example, Irgacure (registered trademark) series commercially available from BASF Corporation includes Irgacure 290, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379. Irgacure 819, Irgacure TPO, Irgacure 1173, and the like.
- Esacure (registered trademark) series commercially available from Lamberti
- Esacure TZM Ezacure TZT
- Ezacure KTO46 Ezacure KTO46
- a known radical polymerization initiator or cationic polymerization initiator may be included.
- the content of the photopolymerization initiator is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, and still more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polymerizable composition. It is.
- the quantum dot-containing composition of the present disclosure may include a polymer.
- the polymer may be a water soluble polymer.
- the water-soluble polymer may be polyvinyl alcohol or an ethylene-vinyl alcohol copolymer.
- Examples of the polymer include poly (meth) acrylate, poly (meth) acrylamide, polyester, polyurethane, polyurea, polyamide, polyether, and polystyrene.
- the quantum dot-containing composition of the present disclosure may contain a viscosity modifier and a silane coupling agent.
- the quantum dot containing composition may contain a viscosity modifier as needed. By adding a viscosity modifier, the quantum dot-containing composition can be adjusted to a desired viscosity.
- the viscosity modifier is preferably a filler having a particle size of 5 nm to 300 nm.
- the viscosity modifier may be a thixotropic agent.
- thixotropic property refers to a property of reducing viscosity in a liquid composition with respect to an increase in shear rate
- a thixotropic agent refers to a thixotropy in a composition by including it in the liquid composition. It refers to a material having a function of imparting sex.
- thixotropic agents include fumed silica, alumina, silicon nitride, titanium dioxide, calcium carbonate, zinc oxide, talc, mica, feldspar, kaolinite (kaolin clay), pyrophyllite (waxite clay), and sericite.
- sericite bentonite, smectite vermiculites (montmorillonite, beidellite, nontronite, saponite, etc.), organic bentonite, organic smectite and the like.
- the quantum dot-containing composition may further contain a silane coupling agent. Since the wavelength conversion layer formed from the polymerizable composition containing the silane coupling agent becomes stronger in adhesion to the adjacent layer by the silane coupling agent, it can exhibit even more excellent light resistance. . This is mainly due to the fact that the silane coupling agent contained in the wavelength conversion layer forms a covalent bond with the surface of the adjacent layer and the constituent components of the layer by hydrolysis reaction or condensation reaction. At this time, it is also preferable to provide an inorganic layer described later as an adjacent layer.
- the silane coupling agent has a reactive functional group such as a radical polymerizable group
- a monomer component constituting the wavelength conversion layer and a cross-linked structure can also be formed, thereby improving the adhesion between the wavelength conversion layer and the adjacent layer. Can contribute.
- the silane coupling agent contained in the wavelength conversion layer is meant to include the silane coupling agent in the form after the reaction as described above.
- silane coupling agent a known silane coupling agent can be used without any limitation.
- a silane coupling agent represented by the general formula (1) described in JP2013-43382A can be exemplified.
- the amount of the additive such as a silane coupling agent is not particularly limited and can be set as appropriate.
- the method for preparing the quantum dot-containing composition is not particularly limited, and may be carried out by a general procedure for preparing a polymerizable composition.
- FIG. 1 is a schematic cross-sectional view of the wavelength conversion member of the present embodiment.
- the wavelength conversion member 1 ⁇ / b> D of the present embodiment includes barrier films 10 and 20 disposed on both main surfaces of the wavelength conversion layer 30 and the wavelength conversion layer 30 obtained by curing the quantum dot-containing composition.
- the “main surface” refers to the surface (front surface, back surface) of the wavelength conversion layer disposed on the viewing side or the backlight side when the wavelength conversion member is used in a display device described later. The same applies to the main surfaces of the other layers and members.
- Each of the barrier films 10 and 20 includes the barrier layers 12 and 22 and the supports 11 and 21 from the wavelength conversion layer 30 side, respectively.
- the details of the wavelength conversion layer 30, the barrier films 10 and 20, the supports 11 and 21, and the barrier layers 12 and 22 will be described.
- Wavelength conversion layer 30 Wavelength conversion layer 30, as shown in FIG. 1, it is excited by being excited by the blue light L B fluorescent quantum dots 30A emits (red light) L R, and the blue light L B in the organic matrix 30P fluorescence quantum dots 30B for emitting (green light) L G is dispersed.
- the quantum dots 30A and 30B are greatly illustrated for easy visual recognition, but actually, for example, the thickness of the wavelength conversion layer 30 is 10 to 100 ⁇ m, and the diameter of the quantum dots is 2 to 7 nm. It is a range.
- the ligand of the present disclosure is coordinated on the surfaces of the quantum dots 30A and 30B.
- the wavelength conversion layer 30 is obtained by curing a quantum dot-containing composition containing quantum dots 30A and 30B coordinated with the ligand of the present disclosure, a polymerizable compound, and a polymerization initiator by light irradiation.
- the organic matrix 30P is formed by curing a polymerizable compound by light irradiation or heat.
- the thickness of the wavelength conversion layer 30 is preferably in the range of 1 to 500 ⁇ m, more preferably in the range of 10 to 100 ⁇ m, and still more preferably in the range of 10 to 50 ⁇ m.
- a thickness of 1 ⁇ m or more is preferable because a high wavelength conversion effect can be obtained. Further, it is preferable that the thickness is 500 ⁇ m or less because the backlight unit can be thinned when incorporated in the backlight unit.
- the wavelength converting layer 30, the quantum dots 30A that emits ultraviolet light L UV by being excited fluorescence (red light) L R in an organic matrix 30P
- the ultraviolet light L UV fluorescent quantum dots 30C for emitting quantum dots 30B for emitting (green light) L G after being excited by the ultraviolet light L UV fluorescent (blue light) L B (not shown) May be dispersed.
- the shape of the wavelength conversion layer is not particularly limited, and can be an arbitrary shape.
- the barrier films 10 and 20 are films having a gas barrier function for blocking oxygen.
- the barrier layers 12 and 22 are provided on the supports 11 and 21, respectively. Due to the presence of the supports 11 and 21, the strength of the wavelength conversion member 1D is improved, and each layer can be easily formed.
- the barrier films 10 and 20 in which the barrier layers 12 and 22 are supported by the supports 11 and 21 are shown. However, the barrier layers 12 and 22 are not supported by the supports 11 and 21. Also good.
- the wavelength conversion member in which the barrier layers 12 and 22 are provided adjacent to both main surfaces of the wavelength conversion layer 30 is shown. However, the supports 11 and 21 have sufficient barrier properties. When it exists, you may form a barrier layer only by the support bodies 11 and 21. FIG.
- the barrier film includes two (barrier film 10 and barrier film 20) in the wavelength conversion member, but may include only one barrier film.
- the barrier films 10 and 20 preferably have a total light transmittance of 80% or more in the visible light region, and more preferably 90% or more.
- the visible light region refers to a wavelength region of 380 to 780 nm, and the total light transmittance indicates an average value of light transmittance over the visible light region.
- the oxygen permeability (also referred to as oxygen permeability) of the barrier films 10 and 20 is preferably 1.00 cm 3 / (m 2 ⁇ day ⁇ atm) or less.
- the oxygen permeability was measured using an oxygen gas permeability measuring device (trade name “OX-TRAN 2/20”, manufactured by MOCON) under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 90%. Value.
- the oxygen permeability of the barrier films 10 and 20 is more preferably 0.10 cm 3 / (m 2 ⁇ day ⁇ atm) or less, and still more preferably 0.01 cm 3 / (m 2 ⁇ day ⁇ atm) or less. .
- the oxygen permeability 1.00 cm 3 / (m 2 ⁇ day ⁇ atm) is 1.14 ⁇ 10 ⁇ 1 fm / Pa ⁇ s when converted to an SI unit system.
- At least one main surface of the wavelength conversion layer 30 is supported by the support 11 or 21.
- this wavelength conversion layer 30 it is preferable that the main surfaces of the front and back of the wavelength conversion layer 30 are supported by the support bodies 11 and 21 like this embodiment.
- the average film thickness of the supports 11 and 21 is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 20 ⁇ m or more and 400 ⁇ m or less, and more preferably 30 ⁇ m or more and 300 ⁇ m or less from the viewpoint of impact resistance of the wavelength conversion member. It is preferable. In an aspect in which retroreflection of light is increased, such as when the concentration of the quantum dots 30A and 30B included in the wavelength conversion layer 30 is reduced, or when the thickness of the wavelength conversion layer 30 is reduced, absorption of light having a wavelength of 450 nm is performed. Since the rate is preferably lower, the average film thickness of the supports 11 and 21 is preferably 40 ⁇ m or less, and more preferably 25 ⁇ m or less from the viewpoint of suppressing a decrease in luminance.
- the support is preferably a transparent support that is transparent to visible light.
- being transparent to visible light means that the light transmittance in the visible light region is 80% or more, preferably 85% or more.
- the light transmittance used as a measure of transparency is measured by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere type light transmittance measuring device. It can be calculated by subtracting the rate.
- paragraphs 0046 to 0052 of JP-A-2007-290369 and paragraphs 0040 to 0055 of JP-A-2005-096108 can be referred to.
- the supports 11 and 21 preferably have an in-plane retardation Re (589) at a wavelength of 589 nm of 1000 nm or less, more preferably 500 nm or less, and even more preferably 200 nm or less.
- Re (589) of the support is in the above range because foreign matters and defects can be more easily found during inspection using a polarizing plate.
- Re (589) can be measured by making light having an input wavelength of 589 nm incident in the normal direction of the film using AxoScan OPMF-1 (manufactured by Optoscience).
- the supports 11 and 21 are preferably supports having a barrier property against oxygen and moisture.
- Preferred examples of the support include a polyethylene terephthalate film, a film made of a polymer having a cyclic olefin structure, and a polystyrene film.
- the barrier layers 12 and 22 are respectively provided with organic layers 12a and 22a and inorganic layers 12b and 22b in this order from the supports 11 and 21 side.
- the organic layers 12 a and 22 a may be provided between the inorganic layers 12 b and 22 b and the wavelength conversion layer 30.
- the barrier layers 12 and 22 are formed by being formed on the surfaces of the supports 11 and 21. Therefore, the barrier films 10 and 20 are comprised by the support bodies 11 and 21 and the barrier layers 12 and 22 provided on it. In the case where the barrier layers 12 and 22 are provided, the support preferably has high heat resistance.
- the layer in the barrier films 10 and 20 adjacent to the wavelength conversion layer 30 may be an inorganic layer or an organic layer, and is not particularly limited.
- the barrier layers 12 and 22 are preferably composed of a plurality of layers because the barrier property can be further enhanced. Therefore, the barrier layers 12 and 22 are preferable from the viewpoint of improving light resistance. However, as the number of layers increases, the light transmission of the wavelength conversion member increases. Since the rate tends to decrease, it is preferable to design in consideration of good light transmittance and barrier properties.
- the inorganic layer is a layer mainly composed of an inorganic material, and is preferably a layer in which the inorganic material occupies 50% by mass or more, more preferably 80% by mass or more, and particularly 90% by mass or more, and is formed only from the inorganic material. Is most preferred.
- the inorganic layers 12b and 22b suitable for the barrier layers 12 and 22 are not particularly limited, and various inorganic compounds such as metals, inorganic oxides, nitrides, and oxynitrides can be used.
- silicon, aluminum, magnesium, titanium, tin, indium and cerium are preferable, and one or more of these may be included.
- the inorganic compound examples include silicon oxide, silicon oxynitride, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, indium oxide alloy, silicon nitride, aluminum nitride, and titanium nitride.
- a metal film such as an aluminum film, a silver film, a tin film, a chromium film, a nickel film, or a titanium film may be provided.
- an inorganic layer containing silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, or aluminum oxide is particularly preferable. Since the inorganic layer made of these materials has good adhesion to the organic layer, even when the inorganic layer has pinholes, the organic layer can effectively fill the pinholes, and the barrier property is further improved. It can be made even higher. Further, silicon nitride is most preferable from the viewpoint of suppressing light absorption in the barrier layer.
- the method for forming the inorganic layer is not particularly limited, and for example, various film forming methods capable of evaporating or scattering the film forming material and depositing it on the deposition surface can be used.
- Examples of the method for forming the inorganic layer include a vacuum evaporation method in which an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is heated and evaporated; an inorganic material is used as a raw material, and oxygen gas is introduced.
- an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is heated and evaporated; an inorganic material is used as a raw material, and oxygen gas is introduced.
- Oxidation reaction vapor deposition method for oxidizing and vapor deposition sputtering method using inorganic material as target raw material, introducing argon gas and oxygen gas and performing sputtering; plasma generated on inorganic material with plasma gun
- chemical vapor deposition methods Physical Vapor Deposition method, PVD method
- ion plating method which are heated by a beam for vapor deposition, or when a silicon oxide vapor deposition film is formed
- a plasma chemical vapor phase using an organosilicon compound as a raw material Growth method (Chemical Vapor Deposition method, CV Law), and the like.
- the thickness of the inorganic layer may be 1 nm to 500 nm, preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm.
- the film thickness of the inorganic layer is within the above range, it is possible to suppress absorption of light in the inorganic layer while realizing good barrier properties, and provide a wavelength conversion member with higher light transmittance. Because it can.
- the organic layer is a layer containing an organic material as a main component, and is preferably a layer in which the organic material occupies 50% by mass or more, further 80% by mass or more, particularly 90% by mass or more.
- the organic layer paragraphs 0020 to 0042 of JP-A-2007-290369 and paragraphs 0074 to 0105 of JP-A-2005-096108 can be referred to.
- the organic layer preferably contains a cardo polymer. This is because the adhesion between the organic layer and the adjacent layer, particularly the adhesion with the inorganic layer, is improved, and a further excellent barrier property can be realized.
- the thickness of the organic layer is preferably in the range of 0.05 ⁇ m to 10 ⁇ m, and more preferably in the range of 0.5 to 10 ⁇ m.
- the thickness of the organic layer is preferably in the range of 0.5 to 10 ⁇ m, and more preferably in the range of 1 to 5 ⁇ m.
- it is preferably in the range of 0.05 ⁇ m to 5 ⁇ m, and more preferably in the range of 0.05 ⁇ m to 1 ⁇ m. This is because when the film thickness of the organic layer formed by the wet coating method or the dry coating method is within the above-described range, the adhesion with the inorganic layer can be further improved.
- the wavelength conversion layer, the inorganic layer, the organic layer, and the support may be laminated in this order, between the inorganic layer and the organic layer, between the two organic layers, or between the two layers.
- a support may be disposed between the inorganic layers and laminated.
- the surface of the barrier film 10 on the side opposite to the surface on the wavelength conversion layer 30 side is preferably provided with an unevenness imparting layer 13 for imparting an uneven structure. It is preferable that the unevenness imparting layer 13 is provided on the barrier film 10 because the blocking property and the slip property can be improved.
- the unevenness providing layer is preferably a layer containing particles. Examples of the particles include inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles. Moreover, although it is preferable that the uneven
- the wavelength conversion member 1D can have a light scattering function in order to efficiently extract the fluorescence of the quantum dots to the outside.
- the light scattering function may be provided inside the wavelength conversion layer 30, or a layer having a light scattering function may be separately provided as the light scattering layer.
- the light scattering layer may be provided on the surface of the barrier layer 22 on the wavelength conversion layer 30 side, or may be provided on the surface of the support opposite to the wavelength conversion layer.
- the unevenness providing layer is preferably a layer that can also be used as a light scattering layer.
- the wavelength conversion layer 30 can be formed by applying the prepared quantum dot-containing composition to the surface of the barrier film 10 or 20 and then curing it by light irradiation or heating.
- Known coating methods include curtain coating, dip coating, spin coating, print coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, and wire bar method. The coating method is mentioned.
- Curing conditions can be appropriately set according to the type of polymerizable compound used and the composition of the quantum dot-containing composition. Moreover, when a quantum dot containing composition is a composition containing a solvent, before hardening, you may give a drying process for solvent removal.
- the curing of the quantum dot-containing composition may be performed in a state where the quantum dot-containing composition is sandwiched between two supports.
- One aspect of the manufacturing process of the wavelength conversion member including the curing process will be described below with reference to FIGS.
- the manufacturing method of the wavelength conversion member in this indication is not limited to the following mode.
- FIG. 2 is a schematic configuration diagram of an example of a manufacturing apparatus for the wavelength conversion member 1D
- FIG. 3 is a partially enlarged view of the manufacturing apparatus shown in FIG.
- the manufacturing apparatus of the present embodiment includes a feeder (not shown), a coating unit 120 that coats the quantum dot-containing composition on the first barrier film 10 to form a coating film (coating film 30M in FIG. 3),
- the second barrier film 20 is bonded onto the film 30M, and the laminate unit 130 that sandwiches the coating film 30M between the first barrier film 10 and the second barrier film 20, and the curing unit 160 that cures the coating film 30M.
- a winder (not shown).
- the manufacturing process of the wavelength conversion member using the manufacturing apparatus shown in FIG. 2 and FIG. 3 is a quantum dot containing composition on the surface of the 1st barrier film 10 (henceforth "1st film”) conveyed continuously.
- at least a step of forming a wavelength conversion layer (cured layer) by wrapping around a roller and irradiating with light while continuously transporting to polymerize and cure the coating film.
- a barrier film having a barrier property against oxygen and moisture is used for both the first film and the second film.
- wavelength conversion member 1D by which both surfaces of the wavelength conversion layer were protected by the barrier film can be obtained.
- a wavelength conversion member having one surface protected by a barrier film may be used, and in that case, the barrier film side is preferably used as the side close to the outside air.
- the first film 10 is continuously conveyed from the unillustrated transmitter to the coating unit 120.
- the first film 10 is delivered from the delivery device at a conveyance speed of 1 to 50 m / min.
- the conveyance speed of the first film 10 is not limited to this conveyance speed.
- a tension of 20 to 150 N / m, preferably 30 to 100 N / m, is applied to the first film 10.
- the quantum dot containing composition (henceforth "application liquid” is also described) is apply
- a die coater 124 and a backup roller 126 disposed to face the die coater 124 are installed.
- the surface opposite to the surface on which the coating film 30M of the first film 10 is formed is wound around the backup roller 126, and the coating liquid is applied from the discharge port of the die coater 124 to the surface of the first film 10 that is continuously conveyed. It is applied to form a coating film 30M.
- the coating film 30 ⁇ / b> M refers to the quantum dot-containing composition before curing applied on the first film 10.
- the die coater 124 to which the extrusion coating method is applied is shown as the coating device in the coating unit 120, but the present invention is not limited to this.
- a coating apparatus to which various methods such as a curtain coating method, a rod coating method, or a roll coating method are applied can be used.
- the first film 10 that has passed through the coating unit 120 and has the coating film 30M formed thereon is continuously conveyed to the laminating unit 130.
- the second film 20 continuously conveyed is laminated on the coating film 30 ⁇ / b> M, and the coating film 30 ⁇ / b> M is sandwiched between the first film 10 and the second film 20.
- a laminating roller 132 and a heating chamber 134 surrounding the laminating roller 132 are installed in the laminating unit 130.
- the heating chamber 134 is provided with an opening 136 for allowing the first film 10 to pass therethrough and an opening 138 for allowing the second film 20 to pass therethrough.
- a backup roller 162 is disposed at a position facing the laminating roller 132.
- the first film 10 on which the coating film 30M is formed is wound around the backup roller 162 on the surface opposite to the surface on which the coating film 30M is formed, and is continuously conveyed to the laminating position P.
- Lamination position P means the position where the contact between the second film 20 and the coating film 30M starts.
- the first film 10 is preferably wound around the backup roller 162 before reaching the laminating position P. This is because even if wrinkles occur in the first film 10, the wrinkles are corrected and removed by the backup roller 162 before reaching the laminate position P.
- the position (contact position) where the first film 10 is wound around the backup roller 162 and the distance L1 to the laminate position P are preferably long, for example, 30 mm or more is preferable, and the upper limit is usually It is determined by the diameter of the backup roller 162 and the pass line.
- the second film 20 is laminated by the backup roller 162 and the laminating roller 132 used in the curing unit 160. That is, the backup roller 162 used in the curing unit 160 is also used as a roller used in the laminating unit 130.
- the present invention is not limited to the above form, and a laminating roller may be installed in the laminating unit 130 in addition to the backup roller 162 so that the backup roller 162 is not used.
- the backup roller 162 used in the curing unit 160 in the laminating unit 130, the number of rollers can be reduced.
- the backup roller 162 can also be used as a heat roller for the first film 10.
- the second film 20 sent from a sending machine (not shown) is wound around the laminating roller 132 and continuously conveyed between the laminating roller 132 and the backup roller 162.
- the second film 20 is laminated on the coating film 30M formed on the first film 10 at the laminating position P. Thereby, the coating film 30 ⁇ / b> M is sandwiched between the first film 10 and the second film 20.
- Lamination refers to laminating the second film 20 on the coating film 30M.
- the distance L2 between the laminating roller 132 and the backup roller 162 is a value of the total thickness of the first film 10, the wavelength conversion layer (cured layer) 30 obtained by polymerizing and curing the coating film 30M, and the second film 20.
- the above is preferable.
- L2 is below the length which added 5 mm to the total thickness of the 1st film 10, the coating film 30M, and the 2nd film 20.
- FIG. By making the distance L2 equal to or less than the total thickness plus 5 mm, it is possible to prevent bubbles from entering between the second film 20 and the coating film 30M.
- the distance L2 between the laminating roller 132 and the backup roller 162 is the shortest distance between the outer circumferential surface of the laminating roller 132 and the outer circumferential surface of the backup roller 162.
- Rotational accuracy of the laminating roller 132 and the backup roller 162 is 0.05 mm or less, preferably 0.01 mm or less in radial runout. The smaller the radial runout, the smaller the thickness distribution of the coating film 30M.
- the difference between the temperature of the backup roller 162 of the curing unit 160 and the temperature of the first film 10 is preferably 30 ° C. or less, more preferably 15 ° C. or less, and most preferably 0 ° C. (that is, the temperature of the film and the backup roller is The same).
- the heating chamber 134 In order to reduce the difference from the temperature of the backup roller 162, when the heating chamber 134 is provided, it is preferable to heat the first film 10 and the second film 20 in the heating chamber 134.
- hot air is supplied to the heating chamber 134 by a hot air generator (not shown), and the first film 10 and the second film 20 can be heated.
- the first film 10 may be heated by the backup roller 162 by being wound around the temperature-adjusted backup roller 162.
- the second film 20 can be heated with the laminating roller 132 by using the laminating roller 132 as a heat roller.
- the heating chamber 134 and the heat roller are not essential, and can be provided as necessary.
- curing in the curing unit 160 is performed by light irradiation, but when the polymerizable compound contained in the quantum dot-containing composition is polymerized by heating, by heating such as blowing hot air. Can be cured.
- a light irradiation device 164 is provided at a position facing the backup roller 162 and the backup roller 162. Between the backup roller 162 and the light irradiation device 164, the first film 10 and the second film 20 sandwiching the coating film 30M are continuously conveyed. What is necessary is just to determine the light irradiated with a light irradiation apparatus according to the kind of photopolymerizable compound contained in a quantum dot containing composition, and an ultraviolet-ray is mentioned as an example.
- the ultraviolet ray means light having a wavelength of 280 to 400 nm.
- a light source that generates ultraviolet rays for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
- the light irradiation amount may be set within a range in which polymerization and curing of the coating film can proceed.
- the coating film 30M can be irradiated with ultraviolet rays having an irradiation amount of 100 to 10,000 mJ / cm 2 .
- the first film 10 is wound around the backup roller 162 in a state where the coating film 30 ⁇ / b> M is sandwiched between the first film 10 and the second film 20, and is continuously conveyed from the light irradiation device 164.
- the wavelength conversion layer 30 can be formed by performing light irradiation to cure the coating film 30M.
- the first film 10 side is wound around the backup roller 162 and continuously conveyed, but the second film 20 may be wound around the backup roller 162 and continuously conveyed.
- Wrapping around the backup roller 162 means a state in which either the first film 10 or the second film 20 is in contact with the surface of the backup roller 162 at a certain wrap angle. Accordingly, the first film 10 and the second film 20 move in synchronization with the rotation of the backup roller 162 while being continuously conveyed.
- the winding around the backup roller 162 may be performed at least in a region irradiated with ultraviolet rays.
- the backup roller 162 includes a cylindrical main body and rotating shafts disposed at both ends of the main body.
- the main body of the backup roller 162 has a diameter of ⁇ 200 to 1000 mm, for example. There is no restriction on the diameter ⁇ of the backup roller 162. In consideration of curl deformation of the laminated film, equipment cost, and rotational accuracy, the diameter is preferably 300 to 500 mm.
- the temperature of the backup roller 162 is determined in consideration of heat generation during light irradiation, curing efficiency of the coating film 30M, and occurrence of wrinkle deformation on the backup roller 162 of the first film 10 and the second film 20. can do.
- the backup roller 162 is preferably set to a temperature range of 10 to 95 ° C., for example, and more preferably 15 to 85 ° C.
- “temperature” with respect to the roller refers to the surface temperature of the roller.
- the distance L3 between the laminate position P and the light irradiation device 164 can be set to 30 mm or more, for example.
- the coating film 30M is cured by the light irradiation to become the wavelength conversion layer 30, and the wavelength conversion member 1D including the first film 10, the wavelength conversion layer 30, and the second film 20 is manufactured.
- the wavelength conversion member 1D is peeled off from the backup roller 162 by being wound around the peeling roller 180.
- the wavelength conversion member 1D is continuously conveyed to a winder (not shown), and then the wavelength conversion member 1D is wound into a roll by the winder.
- FIG. 4 is a schematic cross-sectional view showing the backlight unit.
- the backlight unit 2 includes a light source 1A that emits primary light (blue light L B ) and a light guide plate 1B that guides and emits the primary light emitted from the light source 1A.
- the secondary light (green light L G , red light L R ) composed of this fluorescence and the primary light L B transmitted through the wavelength conversion member 1D are emitted.
- L G, the L R, and L B emits white light Lw from the surface of the retroreflective member 2B.
- the shape of the wavelength conversion member 1D is not particularly limited, and may be an arbitrary shape such as a sheet shape or a bar shape.
- the wavelength conversion member 1D sufficient amount of excitation light (the blue light L B) are, (quantum dots 30A in example 1) quantum dots that emit red light L R, the green light L G-emitting quantum dots ( For example, a necessary amount of fluorescence (green light L G , red light L R ) is emitted by the quantum dots 30B in FIG. 1, and white light L W is emitted from the retroreflective member 2B as the sum of these lights. Is done.
- UV light When ultraviolet light is used as excitation light, light is emitted from the quantum dots 30A by making ultraviolet light incident on the wavelength conversion layer 30 including the quantum dots 30A and 30B in FIG. 1 and 30C (not shown) as excitation light.
- White light can be generated by the red light, the green light emitted by the quantum dots 30B, and the blue light emitted by the quantum dots 30C.
- a backlight unit that has been converted to a multi-wavelength light source.
- blue light having an emission center wavelength in a wavelength band of 430 to 480 nm and a peak of emission intensity having a half width of 100 nm or less, and an emission center wavelength in a wavelength band of 520 to 560 nm, and a half width of It is preferable to emit green light having an emission intensity peak that is 100 nm or less and red light having an emission center wavelength in the wavelength band of 600 to 680 nm and having an emission intensity peak that is 100 nm or less.
- the wavelength band of blue light emitted from the backlight unit is more preferably 440 to 460 nm.
- the wavelength band of the green light emitted from the backlight unit is more preferably 520 to 545 nm.
- the wavelength band of red light emitted from the backlight unit is more preferably 610 to 640 nm.
- the half-value widths of the emission intensity of blue light, green light, and red light emitted from the backlight unit are all preferably 80 nm or less, more preferably 50 nm or less, and 40 nm or less. More preferably, it is more preferably 30 nm or less. Among these, it is particularly preferable that the half-value width of each emission intensity of blue light is 25 nm or less.
- Examples of the light source 1A include those that emit blue light having an emission center wavelength in the wavelength band of 430 nm to 480 nm, and those that emit ultraviolet light.
- a light emitting diode, a laser light source, or the like can be used as the light source 1A.
- the planar light source 1 ⁇ / b> C may be a light source including a light source 1 ⁇ / b> A and a light guide plate 1 ⁇ / b> B that guides and emits primary light emitted from the light source 1 ⁇ / b> A.
- the light source may be a light source that is arranged in a plane parallel to the member 1D and includes a diffusion plate instead of the light guide plate 1B.
- the former light source is generally called an edge light method, and the latter light source is generally called a direct type.
- the edge light method using a light guide plate, a reflection plate, or the like as a constituent member has been described in FIG. 4, but a direct type may be used. Any known light guide plate can be used without any limitation.
- a case where a planar light source is used as the light source has been described as an example.
- a light source other than the planar light source can be used as the light source.
- the wavelength conversion layer preferably includes at least quantum dots 30A that are excited by excitation light and emit red light, and quantum dots 30B that emit green light.
- white light can be generated by the blue light emitted from the light source and transmitted through the wavelength conversion member, and the red light and green light emitted from the wavelength conversion member.
- a light source that emits ultraviolet light having an emission center wavelength in a wavelength band of 300 nm to 430 nm can be used.
- a laser light source can be used instead of the light emitting diode.
- the reflecting plate 2A is not particularly limited, and a known one can be used. Reflectors that can be used as the reflector 2A are described in Japanese Patent No. 3416302, Japanese Patent No. 3363565, Japanese Patent No. 4091978, Japanese Patent No. 3448626, and the contents of these publications are incorporated herein by reference.
- the retroreflective member 2B is composed of a known diffusion plate, diffusion sheet, prism sheet (eg, BEF series manufactured by Sumitomo 3M), reflective polarizing film (eg, DBEF series manufactured by Sumitomo 3M), and the like. Also good.
- the configuration of the retroreflective member 2B is described in Japanese Patent No. 3416302, Japanese Patent No. 3363565, Japanese Patent No. 4091978, Japanese Patent No. 3448626, and the contents of these publications are incorporated herein by reference.
- FIG. 5 shows a schematic cross-sectional view of an example of the liquid crystal display device of the present disclosure.
- the liquid crystal display device 4 includes the backlight unit 2 of the above-described embodiment (FIG. 4) and the liquid crystal cell unit 3 disposed to face the retroreflective member 2 ⁇ / b> B side of the backlight unit 2. It becomes.
- the liquid crystal cell unit 3 has a configuration in which the liquid crystal cell 31 is sandwiched between polarizing plates 32 and 33.
- the polarizing plates 32 and 33 have polarizing plate protective films 321 and 323 on both main surfaces of the polarizers 322 and 332, respectively. A configuration protected by 331 and 333 is employed.
- liquid crystal cell 31 there are no particular limitations on the liquid crystal cell 31, the polarizing plates 32 and 33, and the components thereof that constitute the liquid crystal display device 4, and those produced by known methods and commercially available products can be used without any limitation. It is of course possible to provide a known intermediate layer such as an adhesive layer between the layers.
- the driving mode of the liquid crystal cell 31 is not particularly limited, and is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB). ) And other modes can be used.
- the driving mode of the liquid crystal cell is preferably a VA mode, an OCB mode, an IPS mode, or a TN mode, but is not limited thereto.
- the configuration shown in FIG. 2 of Japanese Patent Application Laid-Open No. 2008-262161 is given as an example.
- the specific configuration of the liquid crystal display device is not particularly limited, and a known configuration can be adopted.
- the liquid crystal display device 4 may further include an associated functional layer such as an optical compensation member that performs optical compensation and an adhesive layer as necessary.
- an associated functional layer such as an optical compensation member that performs optical compensation and an adhesive layer as necessary.
- an optical compensation member that performs optical compensation and an adhesive layer as necessary.
- a surface layer such as a layer may be disposed.
- the polarizing plate 32 on the backlight side may have a retardation film as the polarizing plate protective film 323 on the liquid crystal cell 31 side.
- a retardation film a known cellulose acylate film or the like can be used.
- the backlight unit 2 and the liquid crystal display device 4 include the wavelength conversion layer of the present disclosure that has a high polymerization reaction rate and good curability, the backlight unit 2 and the liquid crystal display device become high brightness.
- barrier film A (Preparation of barrier film A) Using a polyethylene terephthalate (PET) film (trade name “Cosmo Shine (registered trademark) A4300”, thickness 50 ⁇ m, manufactured by Toyobo Co., Ltd.) as a support, an organic layer and an inorganic layer were formed on one side of the support by the following procedure. Sequentially formed.
- PET polyethylene terephthalate
- A4300 thickness 50 ⁇ m, manufactured by Toyobo Co., Ltd.
- Trimethylolpropane triacrylate product name “TMPTA”, manufactured by Daicel Ornex Co., Ltd.
- ESACURE registered trademark
- KTO46 photopolymerization initiator
- the sample was irradiated with ultraviolet rays (integrated irradiation amount: about 600 mJ / cm 2 ) in a nitrogen atmosphere, cured by ultraviolet curing, and wound up.
- the thickness of the organic layer formed on the support was 1 ⁇ m.
- an inorganic layer (silicon nitride layer) was formed on the surface of the organic layer using a roll-to-roll CVD apparatus.
- Silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm), hydrogen gas (flow rate 590 sccm), and nitrogen gas (flow rate 240 sccm) were used as source gases.
- a high frequency power supply having a frequency of 13.56 MHz was used as the power supply.
- the film forming pressure was 40 Pa, and the reached film thickness was 50 nm.
- stacked on the surface of the organic layer formed on the support body was produced.
- a second organic layer was laminated on the surface of the inorganic layer.
- a photopolymerization initiator (trade name “IRGACURE 184”, Ciba Chemical Co., Ltd.) is used with respect to 95.0 parts by mass of urethane skeleton acrylate polymer (trade name “Acryt 8BR930”, manufactured by Taisei Fine Chemical Co., Ltd.). 5.0 parts by mass) were weighed and dissolved in methyl ethyl ketone to prepare a coating solution having a solid concentration of 15%.
- This coating solution was applied directly to the surface of the inorganic layer by roll-to-roll using a die coater, and passed through a 100 ° C. drying zone for 3 minutes. Thereafter, while being held in a heat roll heated to 60 ° C., it was cured by irradiation with ultraviolet rays (integrated irradiation amount: about 600 mJ / cm 2 ) and wound up.
- the thickness of the second organic layer formed on the support was 1 ⁇ m. In this way, a barrier film with a second organic layer (hereinafter referred to as barrier film A) was produced.
- the coating solution was applied by a die coater so that the PET film surface of the barrier film A was a coating surface.
- the wet coating amount was adjusted with a liquid feed pump, and coating was performed at a coating amount of 25 cc / m 2 (the thickness was adjusted to be about 12 ⁇ m with a dry film).
- barrier film B on which the light scattering layer was laminated was obtained.
- the coating solution was applied by a die coater so that the PET film surface of the barrier film A was a coating surface.
- the wet (Wet) coating amount was adjusted with a liquid feed pump, and coating was performed at a coating amount of 10 cc / m 2 . After passing through an 80 ° C. drying zone for 3 minutes, it was wound around a backup roll adjusted to 30 ° C. and cured with ultraviolet rays of 600 mJ / cm 2 and wound up.
- the thickness of the mat layer formed after curing was about 3 to 6 ⁇ m, and the maximum section height Rt (measured based on JIS B0601) had a surface roughness of about 1 to 3 ⁇ m.
- barrier film C on which the uneven layer was laminated was obtained.
- Quantum dot dispersion liquid 1 (luminescence maximum: 535 nm) 20 parts by mass Quantum dot dispersion liquid 2 (luminescence maximum: 630 nm) 2 parts by mass Lauryl methacrylate (trade name “Light Ester L”, manufactured by Kyoeisha Chemical Co., Ltd.) 92.1 parts by mass Ligand LG5 (shown in Table 1) 7 parts by mass Polymerization initiator (Irgacure TPO (trade name), manufactured by BASF) 0.2 parts by mass
- Tables 1 and 2 show the ligands used in the examples and comparative examples.
- Example 3 (Preparation of quantum dot-containing compositions used in Examples 2 to 6 and preparation of coating solutions) It was produced in the same manner as in Example 1 except that the amount of the quantum dot dispersion and the types and amounts of the polymerizable compound and the ligand were changed as shown in Table 3, respectively.
- the polymerizable compound DCP shown in Table 3 is dicyclopentanyl acrylate (trade name “FA-513AS”, manufactured by Hitachi Chemical Co., Ltd.), and A-DCP is tricyclodecane dimethanol diacrylate ( Trade name “A-DCP”, manufactured by Shin-Nakamura Chemical Co., Ltd.
- Example 7 (Preparation of quantum dot-containing composition used in Example 7 and preparation of coating solution)
- INP530-25 (trade name) manufactured by NN-Labs (emission wavelength: 530 nm; hereinafter, quantum dot dispersion 3)
- red quantum dots INP620-25 (trade name) manufactured by NN-Labs Co., Ltd.
- quantum dot dispersion 4 was used as a toluene dispersion of red quantum dots INP620-25 (trade name) manufactured by NN-Labs Co., Ltd.
- quantum dot dispersion 4 transmission wavelength: 620 nm; hereinafter, quantum dot dispersion 4
- a coating liquid used in Example 7 was prepared in the same manner as in Example 2 except that the quantum dot dispersion liquid was changed to the quantum dot disper
- a quantum dot dispersion, a polymerizable compound, a ligand, and a polymerization initiator were produced in the same manner as in Example 1 except that the types and amounts of the dispersion were as shown in Table 3.
- a wavelength conversion member was obtained by the production process described with reference to FIGS. Specifically, the barrier film B is prepared as the first film, and the quantum dot-containing composition 1 prepared above is applied to the die coater on the inorganic layer surface side while continuously transporting at a tension of 1 m / min and 60 N / m. Then, a coating film having a thickness of 50 ⁇ m was formed. Then, the first film on which the coating film is formed is wound around a backup roller, and the second film is laminated on the coating film in such a direction that the inorganic layer surface side is in contact with the coating film.
- the wavelength conversion layer containing quantum dots is formed.
- the irradiation amount of ultraviolet rays was 2000 mJ / cm 2 .
- L1 was 50 mm
- L2 was 1 mm
- L3 was 50 mm.
- a wavelength conversion member was produced in the same manner as in Example 1 except that the coating liquid shown in Table 3 was used and the thickness of the coating film was changed.
- a commercially available tablet terminal equipped with a blue light source in the backlight unit (trade name “Kindle (registered trademark) Fire HDX 7”, manufactured by Amazon, hereinafter simply referred to as “Kindle Fire HDX 7”) may be disassembled and back. The light unit was taken out. Instead of the wavelength conversion film QDEF (Quantum Dot Enhancement Film) incorporated in the backlight unit, the wavelength conversion member of Example or Comparative Example cut into a rectangle was incorporated. In this way, a liquid crystal display device was produced.
- QDEF Quantum Dot Enhancement Film
- the prepared liquid crystal display device was turned on so that the entire surface was displayed in white, and measured with a luminance meter (trade name “SR3”, manufactured by TOPCON) installed at a position of 520 mm perpendicular to the surface of the light guide plate. .
- the luminance Y was evaluated based on the following evaluation criteria. Table 3 shows the measurement results.
- Light ester L lauryl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.
- DCP dicyclopentanyl acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “FA-513AS”
- A-DCP Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “A-DCP”
- IrgTPO IrgacureTPO (polymerization initiator, manufactured by BASF)
- the structural formulas of light ester L, DCP, A-DCP, and Irgacure TPO are shown below.
Abstract
Description
また、特開2011-514879号公報には、表面にリガンドが結合したナノ粒子が開示されている。このリガンドは、X-Sp-Zの式で表され、Xは第1級アミン基、2級アミン基、および尿素等から選択され、Spは、電荷移動させることが可能なスペーサ基であり、Zはナノ粒子に特定の化学反応性を与える反応性基である。反応性基として、チオール基、およびカルボキシル基等が記載されている。
また、本開示は、熱による輝度低下が抑制され、薄手化が可能な波長変換部材、バックライトユニット、および液晶表示装置を提供する。
また、配位子は量子ドットに対し、バインダー樹脂への分散安定性を付与する効果も有している。そのため、量子ドットの表面を効果的に覆うことのできる配位子は、アクリレート樹脂に対する量子ドットの分散安定性を高め、量子ドットの高濃度化を可能にする。
このような知見を基に、本開示は、以下に記載の種々の態様を提供する。
以下、量子ドット含有組成物の詳細について説明する。
量子ドットは、励起光により励起されて蛍光を発光する半導体ナノ粒子である。量子ドット含有組成物は、量子ドットとして発光特性の異なる二種以上の量子ドットを含有してもよい。励起光として青色光を用いた場合には、量子ドット含有組成物は、青色光LBにより励起されて蛍光(赤色光)LRを発光する量子ドット、および青色光LBにより励起されて蛍光(緑色光)LGを発光する量子ドットを含有することができる。
また、励起光として紫外光を用いた場合は、量子ドット含有組成物は、紫外光LUVにより励起されて蛍光(赤色光)LRを発光する量子ドット、紫外光LUVにより励起されて蛍光(緑色光)LGを発光する量子ドット、および紫外光LUVにより励起されて蛍光(青色光)LBを発光する量子ドットを含有することができる。
以下、これらのモノマーの好ましい例について説明する。
ビニルエステル類の例としては、ビニルアセテート、ビニルクロロアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート、および安息香酸ビニルなどが挙げられる。
マレイン酸ジエステル類の例としては、マレイン酸ジメチル、マレイン酸ジエチル、およびマレイン酸ジブチルなどが挙げられる。
フマル酸ジエステル類の例としては、フマル酸ジメチル、フマル酸ジエチル、およびフマル酸ジブチルなどが挙げられる。
イタコン酸ジエステル類の例としては、イタコン酸ジメチル、イタコン酸ジエチル、およびイタコン酸ジブチルなどが挙げられる。
オレフィン類の例としては、エチレン、プロピレン、イソブチレン、ブタジエン、イソプレンなどが挙げられる。
マレイミド類の例としては、マレイミド、ブチルマレイミド、シクロヘキシルマレイミド、フェニルマレイミドなどが挙げられる。
本開示の量子ドット含有組成物における配位子は、公知の合成法によって合成することができる。例えば、特開2007-277514に記載の方法によって合成することができる。
本開示の量子ドット含有組成物は、重合性化合物を含んでもよい。重合性化合物は、アクリル化合物であることが好ましい。重合性化合物としては、単官能又は多官能(メタ)アクリレートモノマーが好ましく、重合性を有していれば、モノマーのプレポリマーやポリマーであってもよい。なお、本明細書において、「(メタ)アクリレート」とは、アクリレートおよびメタクリレートの一方、または両方を意味する。
3官能の(メタ)アクリレートモノマーとしては、ECH変性グリセロールトリ(メタ)アクリレート、EO変性グリセロールトリ(メタ)アクリレート、およびPO変性グリセロールトリ(メタ)アクリレートを挙げることができる。
量子ドット含有組成物は、重合開始剤として、公知の光ラジカル重合開始剤やカチオン重合開始剤を含んでいてもよい。光重合開始剤としては、BASF社から市販されているイルガキュア(Irgacure(登録商標))シリーズでは、例えば、イルガキュア290、イルガキュア651、イルガキュア754、イルガキュア184、イルガキュア2959、イルガキュア907、イルガキュア369、イルガキュア379、イルガキュア819、イルガキュアTPO、イルガキュア1173などが挙げられる。また、ランベルティ(Lamberti)社から市販されているエザキュア(Esacure(登録商標))シリーズでは、例えば、エザキュアTZM、エザキュアTZT、エザキュアKTO46などが挙げられる。その他、公知のラジカル重合開始剤やカチオン重合開始剤を含んでいてもよい。例えば、特開2013-043382号公報の段落0037、特開2011-159924号公報の段落0040~0042を参照できる。
本開示の量子ドット含有組成物は、ポリマーを含んでもよい。ポリマーは水溶性ポリマーであってもよい。水溶性ポリマーは、ポリビニルアルコール、またはエチレン-ビニルアルコール共重合体であってもよい。ポリマーとしては、例えば、ポリ(メタ)アクリレート、ポリ(メタ)アクリルアミド、ポリエステル、ポリウレタン、ポリウレア、ポリアミド、ポリエーテル、およびポリスチレンを挙げることができる。
本開示の量子ドット含有組成物は、粘度調整剤、シランカップリング剤を含有してもよい。
量子ドット含有組成物は、必要に応じて粘度調整剤を含んでもよい。粘度調整剤を添加することによって、量子ドット含有組成物を所望の粘度に調整することが可能である。粘度調整剤は、粒径が5nm~300nmであるフィラーであることが好ましい。また、粘度調整剤はチキソトロピー剤であってもよい。なお、本開示中、チキソトロピー性とは、液状組成物において、せん断速度の増加に対して粘性を減じる性質を指し、チキソトロピー剤とは、それを液状組成物に含ませることによって、組成物にチキソトロピー性を付与する機能を有する素材のことを指す。チキソトロピー剤の具体例としては、ヒュームドシリカ、アルミナ、窒化珪素、二酸化チタン、炭酸カルシウム、酸化亜鉛、タルク、雲母、長石、カオリナイト(カオリンクレー)、パイロフィライト(ろう石クレー)、セリサイト(絹雲母)、ベントナイト、スメクタイト・バーミキュライト類(モンモリロナイト、バイデライト、ノントロナイト、サポナイトなど)、有機ベントナイト、有機スメクタイト等が挙げられる。
量子ドット含有組成物は、さらに、シランカップリング剤を含んでもよい。シランカップリング剤を含む重合性組成物から形成される波長変換層は、シランカップリング剤により隣接する層との密着性が強固なものとなるため、より一層優れた耐光性を示すことができる。これは主に、波長変換層に含まれるシランカップリング剤が、加水分解反応や縮合反応により、隣接する層の表面やその層の構成成分と共有結合を形成することによるものである。このとき、隣接する層として後述の無機層を設けることも好ましい。また、シランカップリング剤がラジカル重合性基等の反応性官能基を有する場合、波長変換層を構成するモノマー成分と架橋構造を形成することも、波長変換層と隣接する層との密着性向上に寄与し得る。なお本明細書において、波長変換層に含まれるシランカップリング剤とは、上記のような反応後の形態のシランカップリング剤も含む意味である。
本実施形態の波長変換部材1Dは、図1に示すように、量子ドット含有組成物を硬化させてなる波長変換層30と波長変換層30の両主面に配置されたバリアフィルム10,20とを備える。ここで、「主表面」とは、波長変換部材を、後述する表示装置に用いた場合の視認側又はバックライト側に配置される波長変換層の表面(おもて面、裏面)をいう。他の層や部材についての主表面も、同様である。バリアフィルム10,20は、それぞれ、波長変換層30側から、それぞれバリア層12,22、および支持体11,21を備える。以下、波長変換層30、バリアフィルム10,20、支持体11,21、およびバリア層12,22の詳細について説明する。
波長変換層30は、図1に示すように、有機マトリックス30P中に青色光LBにより励起されて蛍光(赤色光)LRを発光する量子ドット30A、および青色光LBにより励起されて蛍光(緑色光)LGを発光する量子ドット30Bが分散されてなる。なお、図1において量子ドット30A,30Bは、視認しやすくするために大きく記載してあるが、実際は、例えば、波長変換層30の厚み10~100μmに対し、量子ドットの直径は2~7nmの範囲である。
量子ドット30A,30Bの表面には、本開示の配位子が配位している。波長変換層30は、本開示の配位子が配位した量子ドット30A,30Bと重合性化合物と重合開始剤とを含む量子ドット含有組成物を、光照射によって硬化させてなるものである。
有機マトリックス30Pは、重合性化合物が光照射または熱によって硬化されてなる。
バリアフィルム10,20は、酸素を遮断するガスバリア機能を有するフィルムである。本実施形態では、支持体11,21上にバリア層12,22をそれぞれ備える。支持体11,21の存在により、波長変換部材1Dの強度が向上され、且つ、容易に各層を製膜することができる。
なお、本実施形態では、バリア層12,22が支持体11,21により支持されてなるバリアフィルム10,20について示したが、バリア層12,22は支持体11,21に支持されていなくてもよい。また、本実施形態では、波長変換層30の両主面にバリア層12,22が隣接して備えられている波長変換部材について示したが、支持体11,21がバリア性を充分有している場合は、支持体11,21のみでバリア層を形成してもよい。
波長変換部材1Dにおいて、波長変換層30は、少なくとも一方の主表面が支持体11又は21によって支持されている。波長変換層30は、本実施形態のように、波長変換層30の表裏の主表面を支持体11及び21によって支持されていることが好ましい。
ここで可視光に対して透明とは、可視光領域における光線透過率が、80%以上、好ましくは85%以上であることをいう。透明の尺度として用いられる光線透過率は、JIS-K7105に記載された方法、すなわち積分球式光線透過率測定装置を用いて全光線透過率及び散乱光量を測定し、全光線透過率から拡散透過率を引いて算出することができる。支持体については、特開2007-290369号公報の段落0046~0052、特開2005-096108号公報の段落0040~0055を参照できる。
波長変換部材1Dを作製した後、異物や欠陥の有無を検査する際、2枚の偏光板を消光位に配置し、その間に波長変換部材を差し込んで観察することで、異物や欠陥を見つけやすい。支持体のRe(589)が上記範囲であると、偏光板を用いた検査の際に、異物や欠陥をより見つけやすくなるため、好ましい。
ここで、Re(589)は、AxoScan OPMF-1(オプトサイエンス社製)を用いて、入力波長589nmの光をフィルム法線方向に入射させることにより測定することができる。
バリア層12,22は、支持体11,21側から順に、それぞれ有機層12a,22aと、無機層12b,22bと、を備えてなる。有機層12a,22aは、無機層12b,22bと波長変換層30との間に設けられていてもよい。
無機層とは、無機材料を主成分とする層であり、無機材料が50質量%以上、さらには80質量%以上、特に90質量%以上を占める層が好ましく、無機材料のみから形成される層が最も好ましい。バリア層12,22に好適な無機層12b,22bとしては、特に限定されず、金属、無機酸化物、窒化物、酸化窒化物等の各種無機化合物を用いることができる。無機材料を構成する元素としては、ケイ素、アルミニウム、マグネシウム、チタン、スズ、インジウム及びセリウムが好ましく、これらを一種又は二種以上含んでいてもよい。無機化合物の具体例としては、酸化ケイ素、酸化窒化ケイ素、酸化アルミニウム、酸化マグネシウム、酸化チタン、酸化スズ、酸化インジウム合金、窒化ケイ素、窒化アルミニウム、窒化チタンを挙げることができる。また、無機層として、金属膜、例えば、アルミニウム膜、銀膜、錫膜、クロム膜、ニッケル膜、チタン膜を設けてもよい。
また、バリア層における光の吸収を抑制する観点からは、窒化ケイ素がもっとも好ましい。
有機層とは、有機材料を主成分とする層であって、好ましくは有機材料が50質量%以上、さらには80質量%以上、特に90質量%以上を占める層である。有機層としては、特開2007-290369号公報の段落0020~0042、特開2005-096108号公報の段落0074~0105を参照できる。なお有機層は、カルドポリマーを含むことが好ましい。これにより、有機層と隣接する層との密着性、特に、無機層とも密着性が良好になり、より一層優れたバリア性を実現することができるからである。カルドポリマーの詳細については、上記特開2005-096108号公報の段落0085~0095を参照できる。有機層の膜厚は、0.05μm~10μmの範囲内であることが好ましく、中でも0.5~10μmの範囲内であることが好ましい。有機層がウェットコーティング法により形成される場合には、有機層の膜厚は、0.5~10μmの範囲内、中でも1μm~5μmの範囲内であることが好ましい。また、ドライコーティング法により形成される場合には、0.05μm~5μmの範囲内、中でも0.05μm~1μmの範囲内であることが好ましい。ウェットコーティング法又はドライコーティング法により形成される有機層の膜厚が上述した範囲内であることにより、無機層との密着性をより良好なものとすることができるからである。
波長変換層30側の面と反対側のバリアフィルム10の面には、凹凸構造を付与する凹凸付与層13が設けられていることが好ましい。バリアフィルム10上に凹凸付与層13が設けられていると、ブロッキング性、滑り性を改良することができるため、好ましい。凹凸付与層は粒子を含有する層であることが好ましい。粒子としては、シリカ、アルミナ、酸化金属等の無機粒子、あるいは架橋高分子粒子等の有機粒子等が挙げられる。また、凹凸付与層は、バリアフィルムの波長変換層とは反対側の表面に設けられることが好ましいが、両面に設けられていてもよい。
次に、波長変換層30の両面に、支持体11,21上にバリア層12,22を備えたバリアフィルム10,20を有する態様の波長変換部材1Dの製造方法の一例を説明する。
本実施形態において、波長変換層30は、調製した量子ドット含有組成物をバリアフィルム10または20の表面に塗布した後に光照射、又は加熱により硬化させ、形成することができる。塗布方法としてはカーテンコーティング法、ディップコーティング法、スピンコーティング法、印刷コーティング法、スプレーコーティング法、スロットコーティング法、ロールコーティング法、スライドコーティング法、ブレードコーティング法、グラビアコーティング法、ワイヤーバー法等の公知の塗布方法が挙げられる。
本実施態様の製造装置は、図示しない送出機と、第一のバリアフィルム10上に量子ドット含有組成物を塗布して塗膜(図3における塗膜30M)を形成する塗布部120と、塗膜30M上に第二のバリアフィルム20を貼り合わせて、塗膜30Mを第一のバリアフィルム10と第二のバリアフィルム20とで挟持するラミネート部130と、塗膜30Mを硬化する硬化部160と、図示しない巻き取り機とを備える。
次に、本開示の波長変換部材を備えたバックライトユニットの一例について説明する。図4は、バックライトユニットを示す概略構成断面図である。
図4に示されるように、バックライトユニット2は、一次光(青色光LB)を出射する光源1Aと光源1Aから出射された一次光を導光させて出射させる導光板1Bとからなる面状光源1Cと、面状光源1C上に備えられてなる波長変換部材1Dと、波長変換部材1Dを挟んで面状光源1Cと対向配置される再帰反射性部材2Bと、面状光源1Cを挟んで波長変換部材1Dと対向配置される反射板2Aとを備えており、波長変換部材1Dは、面状光源1Cから出射された一次光LBの少なくとも一部を励起光として、蛍光を発光し、この蛍光からなる二次光(緑色光LG,赤色光LR)及び波長変換部材1Dを透過した一次光LBを出射するものである。LG、LR、およびLBにより、再帰反射性部材2Bの表面から白色光Lwを出射する。
波長変換部材1Dの形状は特に限定されるものではなく、シート状、バー状等の任意の形状であることができる。
さらなる輝度および色再現性の向上の観点から、バックライトユニットが発光する青色光の波長帯域は、440~460nmであることがより好ましい。
同様の観点から、バックライトユニットが発光する緑色光の波長帯域は、520~545nmであることがより好ましい。
また、同様の観点から、バックライトユニットが発光する赤色光の波長帯域は、610~640nmであることがより好ましい。
バックライトユニットの構成としては、図4では、導光板や反射板などを構成部材とするエッジライト方式について説明したが、直下型方式であっても構わない。導光板としては、公知のものを何ら制限なく使用することができる。
なお、本実施形態では、光源として面状光源を用いた場合を例に説明したが、光源としては面状光源以外の光源も使用することができる。
また他の態様では、発光ダイオードに替えてレーザー光源を使用することもできる。
上述のバックライトユニット2は液晶表示装置に応用することができる。図5に、本開示の液晶表示装置の一例の概略構成断面図を示す。
図5に示されるように、液晶表示装置4は、上記実施形態(図4)のバックライトユニット2とバックライトユニット2における再帰反射性部材2B側に対向配置された液晶セルユニット3とを備えてなる。液晶セルユニット3は、液晶セル31を偏光板32と33とで挟持した構成であり、偏光板32,33は、それぞれ、偏光子322、332の両主面を偏光板保護フィルム321と323、331と333で保護した構成としている。
支持体としてポリエチレンテレフタレート(PET)フィルム(東洋紡社製、商品名「コスモシャイン(登録商標)A4300」、厚さ50μm)を用いて、支持体の片面側に以下の手順で有機層および無機層を順次形成した。
トリメチロールプロパントリアクリレート(製品名「TMPTA」、ダイセル・オルネクス(株)製)および光重合開始剤(商品名「ESACURE(登録商標) KTO46」、ランベルティ社製)を用意し、質量比率として95:5となるように秤量し、これらをメチルエチルケトンに溶解させ、固形分濃度15%の塗布液とした。この塗布液を、ダイコーターを用いてロールトウロールにてPETフィルム上に塗布し、50℃の乾燥ゾーンを3分間通過させた。その後、窒素雰囲気下で紫外線を照射(積算照射量約600mJ/cm2)し、紫外線硬化にて硬化させ、巻き取った。支持体上に形成された有機層の厚さは、1μmであった。
次に、ロールトウロールのCVD装置を用いて、有機層の表面に無機層(窒化ケイ素層)を形成した。原料ガスとして、シランガス(流量160sccm)、アンモニアガス(流量370sccm)、水素ガス(流量590sccm)、および窒素ガス(流量240sccm)を用いた。電源として、周波数13.56MHzの高周波電源を用いた。製膜圧力は40Pa、到達膜厚は50nmであった。このようにして支持体上に形成された有機層の表面に無機層が積層されたバリアフィルムを作製した。
光散乱粒子として、シリコーン樹脂粒子(商品名「トスパール120」、モメンティブ社製、平均粒子サイズ2.0μm)150gおよびポリメチルメタクリレート(PMMA)粒子 (積水化学社製テクポリマー、平均粒子サイズ8μm)40gをメチルイソブチルケトン(MIBK)550gでまず1時間ほど攪拌し、分散させて分散液を得た。得られた分散液に、アクリレート系化合物(大阪有機合成社製Viscoat700HV)50g、アクリレート系化合物(商品名「8BR500」、大成ファインケミカル社製)40gを加え、さらに攪拌した。光重合開始剤(商品名「イルガキュア(登録商標)819」、BASF社製)1.5gおよびフッ素系界面活性剤(商品名「FC4430」、3M社製)0.5gをさらに添加して塗布液(光散乱層形成用重合性組成物)を作製した。
上記のバリアフィルムAのPETフィルム表面が塗布面になるように、上記塗布液をダイコーターにて塗布した。湿潤(Wet)塗布量を送液ポンプで調整し、塗布量25cc/m2で塗布を行った(乾燥膜で12μm程度になるように厚みを調整した)。60℃の乾燥ゾーンを3分間で通過させた後に30℃に調整したバックアップロールに巻き付け600mJ/cm2の紫外線で硬化した後に巻き取った。こうして、光散乱層が積層されたバリアフィルムBを得た。
-マット層形成用重合性組成物の調製-
マット層の凹凸を形成する粒子として、シリコーン樹脂粒子(商品名「トスパール2000b」、モメンティブ社製、平均粒子サイズ6.0μm)190gをメチルエチルケトン(MEK)4700gでまず1時間ほど攪拌し、分散させて分散液を得た。得られた分散液に、アクリレート系化合物(商品名「A-DPH」、新中村化学工業)430g、アクリレート系化合物(商品名「8BR930」、大成ファインケミカル社製)800gを加え、さらに攪拌した。光重合開始剤(商品名「イルガキュア(登録商標)184」、BASF社製)40gを添加して塗布液を作製した。
上記のバリアフィルムAのPETフィルム表面が塗布面になるように、上記塗布液をダイコーターにて塗布した。湿潤(Wet)塗布量を送液ポンプで調整し、塗布量10cc/m2で塗布を行った。80℃の乾燥ゾーンを3分間で通過させた後に30℃に調整したバックアップロールに巻き付け600mJ/cm2の紫外線で硬化した後に巻き取った。硬化後に形成されたマット層の厚さは3~6μ程度であり、最大断面高さRt(JIS B0601に基づいて測定した。)が1~3μm程度の表面粗さを有していた。こうして、凹凸層が積層されたバリアフィルムCを得た。
実施例1で使用する緑色量子ドットのトルエン分散液として、NN-ラボズ社製CZ520-100(商品名)(発光波長535nm。以下、量子ドット分散液1。)、赤色量子ドットのトルエン分散液として、NN-ラボズ社製CZ620-100(商品名)(発光波長630nm。以下、量子ドット分散液2。)を用いた。これらはいずれもコアとしてCdSe、シェルとしてZnS、及び配位子としてオクタデシルアミンを用いた量子ドットであり、トルエンに3重量%の濃度で分散されていた。
20質量部の量子ドット分散液1と、2質量部の量子ドット分散液2を混合し、40度、0.03気圧で15分間減圧し、トルエンを除去した。その後、下記の量子ドット含有組成物1の組成比となるよう、重合性化合物(ラウリルメタクリレート)、配位子(LG5)、および重合開始剤(IrgacureTPO)を窒素雰囲気下にて調製し、孔径0.2μmのポリプロピレン製フィルタでろ過した後、塗布液として用いた。
量子ドット分散液1(発光極大:535nm) 20質量部
量子ドット分散液2(発光極大:630nm) 2質量部
ラウリルメタクリレート(商品名「ライトエステルL」、共栄社化学(株)製)
92.1質量部
配位子LG5(表1に示す) 7質量部
重合開始剤(IrgacureTPO(商品名),BASF社製)
0.2質量部
量子ドット分散液の量と、重合性化合物および配位子の種類および量をそれぞれ表3に示したとおりに変更した以外は、実施例1と同様に作製した。
ただし、表3に記載の重合性化合物DCPは、ジシクロペンタニルアクリレート(商品名「FA-513AS」、日立化成(株)製)であり、A-DCPは、トリシクロデカンジメタノールジアクリレート(商品名「A-DCP」、新中村化学工業(株)製)である。
実施例7で使用する緑色量子ドットのトルエン分散液として、NN-ラボズ社製INP530-25(商品名)(発光波長530nm。以下、量子ドット分散液3。)、赤色量子ドットのトルエン分散液として、NN-ラボズ社製INP620-25(商品名)(発光波長620nm。以下、量子ドット分散液4。)を用いた。これらはいずれもコアとしてInP、シェルとしてZnS、及び配位子としてオレイルアミンを用いた量子ドットであり、トルエンに3重量%の濃度で分散されていた。
量子ドット分散液を量子ドット分散液3および量子ドット分散液4に変更した以外は、実施例2と同様にして、実施例7で使用する塗布液を作製した。
量子ドット分散液、重合性化合物、配位子、および重合開始剤の種類および量を、表3に示したとおりにした以外は、実施例1と同様に作製した。
上述した手順で作製したバリアフィルムBを第一のフィルム、およびバリアフィルムCを第二のフィルムとして使用し、図2および図3を参照して説明した製造工程により、波長変換部材を得た。具体的には、第一のフィルムとしてバリアフィルムBを用意し、1m/分、60N/mの張力で連続搬送しながら、無機層面側に上記で調製した量子ドット含有組成物1をダイコーターにて塗布し、50μmの厚さの塗膜を形成した。次いで、塗膜が形成された第一のフィルムをバックアップローラに巻きかけ、塗膜の上に第二のフィルムを無機層面側が塗膜に接する向きでラミネートし、バリアフィルムB、およびバリアフィルムCで塗膜を挟持した状態で連続搬送しながら、160W/cmの空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて、紫外線を照射して硬化させ、量子ドットを含有する波長変換層を形成した。紫外線の照射量は2000mJ/cm2であった。また、図3におけるL1は50mm、L2は1mm、L3は50mmであった。
表3に記載の塗布液を用い、塗膜の厚さを変更した以外は、実施例1と同様にして波長変換部材を作製した。
バックライトユニットに青色光源を備える市販のタブレット端末(商品名「Kindle(登録商標)Fire HDX 7」、Amazon社製、以下、単にKindle Fire HDX 7と記載する場合がある。)を分解し、バックライトユニットを取り出した。バックライトユニットに組み込まれていた波長変換フィルムQDEF(Quantum Dot Enhancement Film)に代えて矩形に切り出した実施例または比較例の波長変換部材を組み込んだ。このようにして液晶表示装置を作製した。作製した液晶表示装置を点灯させ、全面が白表示になるようにし、導光板の面に対して垂直方向520mmの位置に設置した輝度計(商品名「SR3」、TOPCON社製)にて測定した。そして輝度Yを下記評価基準に基づいて評価した。測定結果を表3に示す。
作成した波長変換部材を、ヤマト科学株式会社製精密恒温器DF411を用い、85℃で1000時間加熱した。その後、上記と同様にしてKindle Fire HDX 7に組み込み、輝度を測定した。
耐熱性を、下記評価基準に基づいて評価した。測定結果を表3に示す。
<評価基準>
AA:上記加熱による輝度の低下が5%未満
A:上記加熱による輝度の低下が5%以上15%未満
B:上記加熱による輝度の低下が15%以上30%未満
C:上記加熱による輝度の低下が30%以上50%未満
D:上記加熱による輝度の低下が50%以上
ライトエステルL:ラウリルメタクリレート,共栄社化学(株)製
DCP:ジシクロペンタニルアクリレート、日立化成(株)製、商品名「FA-513AS」
A-DCP:トリシクロデカンジメタノールジアクリレート、新中村化学工業(株)製、商品名「A-DCP」
IrgTPO:IrgacureTPO(重合開始剤,BASF社製)
以下に、ライトエステルL、DCP、A-DCP、Irgacure TPOの構造式を示す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
1A 光源
1B 導光板
1C 面状光源
1D 波長変換部材
2 バックライトユニット
2A 反射板
2B 再帰反射性部材
3 液晶セルユニット
4 液晶表示装置
10,20 バリアフィルム
11,21 支持体
12,22バリア層
12a,22a 有機層
12b,22b 無機層
13 凹凸付与層(マット層)
30 波長変換層
30A,30B 量子ドット
30P 有機マトリックス
31 液晶セル
LB 励起光(一次光、青色光)
LR 赤色光(二次光、蛍光)
LG 緑色光(二次光、蛍光)
LW 白色光
Claims (13)
- 量子ドットと、該量子ドットの表面に配位する配位性基を有する配位子とを含み、該配位子が下記一般式Iで表される量子ドット含有組成物:
一般式I中、Aは、アミノ基、カルボキシ基、メルカプト基、ホスフィン基、およびホスフィンオキシド基から選ばれる前記配位性基を1つ以上含む有機基であり、Zは、(n+m+l)価の有機連結基であり、Rは、置換基を有してもよいアルキル基、アルケニル基またはアルキニル基を含む基であり、Yは、重合度が3以上であって、ポリアクリレート骨格、ポリメタクリレート骨格、ポリアクリルアミド骨格、ポリメタクリルアミド骨格、ポリエステル骨格、ポリウレタン骨格、ポリウレア骨格、ポリアミド骨格、ポリエーテル骨格、およびポリスチレン骨格から選ばれる少なくとも1種の骨格を含む高分子鎖を有する基である;nおよびmは、各々独立に1以上の数であり、lは0以上の数であり、n+m+lは3以上の整数である;n個のAは、同一であっても異なっていてもよい;m個のYは、同一であっても異なっていてもよい;l個のRは、それぞれ同一であっても異なっていてもよい;ただし、前記配位性基は分子中に少なくとも2つ含まれる。 - 重合性化合物をさらに含む請求項1から請求項3のうちいずれか1項記載の量子ドット含有組成物。
- 少なくとも1つのポリマー、および少なくとも1つの溶媒をさらに含む請求項1から請求項4のうちいずれか1項記載の量子ドット含有組成物。
- 前記ポリマーが、水溶性ポリマーである請求項5記載の量子ドット含有組成物。
- 前記水溶性ポリマーが、ポリビニルアルコール、またはエチレン-ビニルアルコール共重合体である請求項6記載の量子ドット含有組成物。
- 前記量子ドットは、600nm~680nmの波長帯域に発光中心波長を有する量子ドット、520nm~560nmの波長帯域に発光中心波長を有する量子ドット、および430nm~480nmの波長帯域に発光中心波長を有する量子ドットから選択される少なくとも一種である請求項1から請求項7のうちいずれか1項記載の量子ドット含有組成物。
- 請求項1から請求項8のうちいずれか1項記載の量子ドット含有組成物を硬化させてなる波長変換層を有する波長変換部材。
- さらに、酸素透過度が1.00cm3/m2・day・atm以下であるバリアフィルムを有し、前記波長変換層の2つの主表面の少なくとも一方が、前記バリアフィルムに接している請求項9記載の波長変換部材。
- 前記バリアフィルムを2つ有し、前記波長変換層の2つの主表面が、それぞれ前記バリアフィルムに接している請求項10記載の波長変換部材。
- 少なくとも請求項9から請求項11のうちいずれか1項記載の波長変換部材と光源とを備えるバックライトユニット。
- 少なくとも請求項12記載のバックライトユニットと液晶セルとを備える液晶表示装置。
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KR20190020041A (ko) | 2019-02-27 |
CN109476989A (zh) | 2019-03-15 |
JP6713048B2 (ja) | 2020-06-24 |
KR102151510B1 (ko) | 2020-09-03 |
US11535761B2 (en) | 2022-12-27 |
US20190144689A1 (en) | 2019-05-16 |
CN109476989B (zh) | 2022-03-08 |
JPWO2018016589A1 (ja) | 2019-03-07 |
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