JP2019218422A - Ink composition set, photoconversion layer and color filter - Google Patents

Abstract

To provide an ink composition set used for the production of a color filter that can reduce a color change in a viewing angle.SOLUTION: An ink composition set contains at least one light-emitting ink composition containing a light-emitting nano crystal particle, and a non-light-emitting ink composition containing a light-scattering particle.SELECTED DRAWING: None

Description

  The present invention relates to an ink composition set, a light conversion layer, and a color filter.

  Conventionally, a pixel portion (color filter pixel portion) in a display such as a liquid crystal display device is, for example, a curable resist containing red organic pigment particles or green organic pigment particles, and an alkali-soluble resin and / or an acrylic monomer. It has been manufactured by photolithography using materials.

  In recent years, there has been a strong demand for lower power consumption of displays, and instead of the red organic pigment particles or green organic pigment particles, for example, quantum dots, quantum rods, luminescent nanocrystalline particles such as other inorganic phosphor particles, etc. A method of forming a pixel portion such as a red pixel and a green pixel by using is being actively researched.

  By the way, when using a color filter having a pixel portion formed using the luminescent nanocrystalline particles, in order to sufficiently exhibit the luminescent properties of the luminescent nanocrystalline particles, typically, the luminescent nanocrystalline particles A light source (backlight) that emits light having a peak wavelength in the absorption wavelength range is preferably used. Therefore, light from a light source can be used as it is by making a part of the plurality of pixel portions in the color filter a transparent pixel portion that does not contain luminescent nanocrystal particles (for example, see Patent Document 1). .

JP-A-2006-81055

  However, as a result of the study by the present inventors, it has been clarified that a display using a color filter having the transparent pixel portion has a large color change at a viewing angle and is inferior in color reproducibility.

  Therefore, an object of the present invention is to provide a color filter capable of reducing color change at a viewing angle, a light conversion layer used for the color filter, and an ink composition set for forming the light conversion layer. I do.

  One aspect of the present invention relates to an ink composition set including at least one luminescent ink composition containing luminescent nanocrystalline particles and a non-luminescent ink composition containing light scattering particles.

  According to the ink composition set of the present invention, a color filter capable of reducing a color change at a viewing angle can be manufactured. The present inventors presume the reason for obtaining such an effect as follows.

  That is, the luminescent nanocrystal particles typically emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength in all directions by absorbing light having a predetermined wavelength. Therefore, when the light having the predetermined wavelength is incident on the pixel portion containing the luminescent nanocrystal particles, the intensity of the light emitted from the pixel portion containing the luminescent nanocrystal particles is substantially uniform regardless of the viewing angle. It becomes. On the other hand, in the pixel portion that does not contain the light-emitting nanocrystal particles, the incident light travels straight without being absorbed by the light-emitting nanocrystal particles, so that the light is emitted from the pixel portion with the front direction toward the display as the traveling direction. Therefore, in a display using a conventional color filter including a pixel portion containing luminescent nanocrystal particles and a transparent pixel portion not containing luminescent nanocrystal particles, the display is viewed obliquely with respect to the display. In the emitted light, the light intensity in the wavelength range of the light from the light source decreases. This causes a color change at the viewing angle. On the other hand, in the ink composition set of the present invention, since the non-light-emitting ink composition contains light-scattering particles, light incident on the pixel portion formed of the non-light-emitting ink composition is scattered in the pixel portion, Light is also emitted obliquely to the display. For these reasons, according to the ink composition set of the present invention, it is possible to manufacture a color filter capable of reducing a color change at a viewing angle.

  The ink composition set includes, as the at least one luminescent ink composition, luminescent nanocrystalline particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. And a second luminescent nanocrystal particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having an emission peak wavelength in the range of 500 to 560 nm. A luminescent ink composition.

  The average particle size of the light scattering particles is preferably 80 nm or more.

  The light-scattering particles preferably have a refractive index of 1.5 or more.

  The light scattering particles are preferably titanium oxide particles.

  The luminescent ink composition and the non-luminescent ink composition may further contain a photopolymerizable compound and / or a thermosetting resin.

  The above ink composition set can be used for forming a light conversion layer. That is, the ink composition set of the present invention may be an ink composition set for forming a light conversion layer.

  The above-mentioned ink composition set may be an ink composition set (ink-jet ink set) used in an ink-jet method.

  One aspect of the present invention relates to a light conversion layer including at least one kind of luminescent pixel portion containing luminescent nanocrystal particles and a non-luminescent pixel portion containing light scattering particles.

  According to the light conversion layer of the present invention, a color filter capable of reducing a color change at a viewing angle can be manufactured.

  The light conversion layer contains, as the at least one kind of luminescent pixel portion, luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. And a second luminescent pixel containing luminescent nanocrystalline particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. And a unit.

  The average particle size of the light scattering particles is preferably 80 nm or more.

  The light-scattering particles preferably have a refractive index of 1.5 or more.

  The light scattering particles are preferably titanium oxide particles.

  The light-emitting pixel portion and the non-light-emitting pixel portion may further contain a curing component including a polymer of a photopolymerizable compound and / or a cured product of a thermosetting resin.

  One aspect of the present invention relates to a color filter including the above-described light conversion layer.

  ADVANTAGE OF THE INVENTION According to this invention, the color filter which can reduce the color change in a viewing angle, the light conversion layer used for the said color filter, and the ink composition set for forming the said light conversion layer can be provided.

FIG. 1 is a schematic sectional view of a color filter according to one embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail.

<Ink composition set>
In one embodiment, the ink composition set includes at least one luminescent ink composition containing luminescent nanocrystalline particles and a non-luminescent ink composition containing light scattering particles. An ink composition set according to an embodiment is used for forming a light conversion layer (for example, a color filter) used for forming a pixel portion of a light conversion layer included in a color filter or the like by a photolithography method, an inkjet method, or the like. 2) is an ink composition set.

  The ink composition set of one embodiment can be applied as an ink set used in a known and commonly used method of manufacturing a color filter, but wastefully consumes relatively expensive materials such as luminescent nanocrystal particles and a solvent. Instead, it is possible to form a pixel portion (light conversion layer) only by using a necessary amount in a necessary place, and therefore, it is necessary to appropriately prepare and use the pixel portion (light conversion layer) so that it is more suitable for an inkjet system than for a photolithography system. preferable.

  Each ink composition in the ink composition set of one embodiment contains, for example, a photopolymerizable compound and / or a thermosetting resin. When a pixel portion containing luminescent nanocrystal particles is formed by an inkjet method using a conventional ink composition, both excellent ejection stability and excellent optical characteristics (for example, an effect of suppressing a decrease in external quantum efficiency) are achieved. Although it was difficult, according to the luminescent ink composition in the ink composition set of one embodiment, it is possible to achieve both excellent ejection stability and excellent optical characteristics even in the inkjet method. . That is, the ink composition set of one embodiment is suitably used for the purpose of forming a pixel portion (for example, a color filter pixel portion) by an inkjet method.

  Hereinafter, an ink composition set for a color filter (an inkjet ink set for a color filter) used in an ink jet system will be described as an example.

(Luminescent ink composition)
The luminescent ink composition contains, for example, luminescent nanocrystalline particles, and a photopolymerizable compound and / or a thermosetting resin.

[Luminescent nanocrystalline particles]
Luminescent nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have a maximum particle diameter of 100 nm or less measured by a transmission electron microscope or a scanning electron microscope, for example. It is a crystal.

  The luminescent nanocrystal particles can emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength, for example, by absorbing light having a predetermined wavelength. The luminescent nanocrystal particles may be red luminescent nanocrystal particles (red luminescent nanocrystal particles) that emit light having a luminescence peak wavelength in the range of 605 to 665 nm (red light). It may be green light-emitting nanocrystal particles (green light-emitting nanocrystal particles) that emit light (green light) having an emission peak wavelength in the range, and light (blue light) having an emission peak wavelength in the range of 420 to 480 nm. ) That emit blue light-emitting nanocrystal particles (blue light-emitting nanocrystal particles). In the present embodiment, the luminescent ink composition preferably includes at least one of these luminescent nanocrystal particles. The light absorbed by the luminescent nanocrystal particles is, for example, light (blue light) having a wavelength in the range of 400 nm or more and less than 500 nm (particularly, light having a wavelength in the range of 420 to 480 nm) or in the range of 200 nm to 400 nm. (Ultraviolet light). Note that the emission peak wavelength of the luminescent nanocrystal particles can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using a spectrofluorometer.

  When the ink composition set of the present embodiment includes a plurality of luminescent ink compositions, luminescent nanocrystals that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm A first luminescent ink composition containing particles, and a second luminescent nanocrystal particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having an emission peak wavelength in the range of 500 to 560 nm. Is preferable.

  The red-emitting nanocrystalline particles are 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less, 643 nm or less, 640 nm or less, 637 nm or less, 635 nm or less. , 632 nm or less, or 630 nm or less, and preferably 628 nm, 625 nm, 623 nm, 620 nm, 615 nm, 610 nm, 607 nm or more, or 605 nm or more. These upper and lower limits can be arbitrarily combined. In the following description, the upper limit and the lower limit individually described can be arbitrarily combined.

  The green-emitting nanocrystalline particles have an emission peak wavelength at 560 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less, 532 nm or less, or 530 nm or less. It is preferable that the emission peak wavelength be at least 528 nm, at least 525 nm, at least 523 nm, at least 520 nm, at least 515 nm, at least 510 nm, at least 507 nm, at least 505 nm, at least 503 nm, or at least 500 nm.

  The blue-emitting nanocrystalline particles have an emission peak wavelength at 480 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less, 452 nm or less, or 450 nm or less. It is preferable to have an emission peak wavelength at 450 nm or more, 445 nm or more, 440 nm or more, 435 nm or more, 430 nm or more, 428 nm or more, 425 nm or more, 422 nm or more, or 420 nm or more.

  According to the solution of the Schrodinger wave equation of the well-type potential model, the wavelength (emission color) of light emitted from the luminescent nanocrystal particles depends on the size (eg, particle diameter) of the luminescent nanocrystal particles. It also depends on the energy gap of the crystal grains. Therefore, the emission color can be selected by changing the constituent material and size of the luminescent nanocrystal particles used.

  The luminescent nanocrystal particles may be luminescent nanocrystal particles containing a semiconductor material (luminescent semiconductor nanocrystal particles). Examples of the luminescent semiconductor nanocrystal particles include quantum dots and quantum rods. Among these, quantum dots are preferred from the viewpoint that the emission spectrum can be easily controlled, the reliability is ensured, the production cost is reduced, and the mass productivity is improved.

  The light-emitting semiconductor nanocrystal particles may include only a core including the first semiconductor material, and include a core including the first semiconductor material, and a second semiconductor material different from the first semiconductor material. And a shell covering at least a part of the core. In other words, the structure of the luminescent semiconductor nanocrystal particles may be a structure composed of only the core (core structure) or a structure composed of the core and the shell (core / shell structure). In addition, the luminescent semiconductor nanocrystal particles include a third semiconductor material different from the first and second semiconductor materials, in addition to the shell (first shell) including the second semiconductor material, and A shell (second shell) covering at least a part thereof may be further provided. In other words, the structure of the luminescent semiconductor nanocrystal particles may be a structure including a core, a first shell, and a second shell (core / shell / shell structure). Each of the core and the shell may be a mixed crystal containing two or more semiconductor materials (for example, CdSe + CdS, CIS + ZnS, etc.).

  The luminescent nanocrystal particles are selected as a semiconductor material from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors and I-II-IV-VI semiconductors. It is preferable to include at least one semiconductor material.

Specific semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeD, HgSeTe, HgSed, HgSeTe, HgSeC, ZnSe CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSZn, Al, ZnH, ZnH InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, Ga Sb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInP, InP, InP, InP InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe 2, CuGaSe _2, CuInS _2, CuG _{S 2, CuInSe 2, AgInS 2} , AgGaSe 2, AgGaS 2, C, include Si and Ge. The light-emitting semiconductor nanocrystal particles can easily control the emission spectrum, reduce the production cost while securing the reliability, and improve the mass productivity, from the viewpoint that CdS, CdSe, CdTe, ZnS, _{ZnSe, ZnTe, ZnO, HgS,} HgSe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS 2, AgInSe 2, AgInTe 2, AgGaS 2, AgGaSe 2, AgGaTe 2, CuInS 2, CuInSe 2, CuInTe 2 , CuGaS ₂ , CuGaSe ₂ , CuGaTe ₂ , Si, C, Ge, and at least one selected from the group consisting of Cu ₂ ZnSnS ₄ .

  The red light-emitting semiconductor nanocrystal particles include, for example, CdSe nanocrystal particles and nanocrystal particles having a core / shell structure, in which the shell portion is CdS and the inner core portion is CdSe. Nanocrystal particles having a core / shell structure, wherein the shell portion is CdS and the inner core portion is ZnSe, a nanocrystal particle of a mixed crystal of CdSe and ZnS, a nanocrystal particle of InP. A crystalline particle, a nanocrystalline particle having a core / shell structure, wherein the shell portion is ZnS and the inner core portion is InP, a nanocrystalline particle having a core / shell structure, Nanocrystalline particles in which the shell portion is a mixed crystal of ZnS and ZnSe and the inner core portion is InP, nanocrystalline particles of a mixed crystal of CdSe and CdS, ZnSe and Cd And a nanocrystal particle having a core / shell / shell structure, wherein the first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is Nanocrystalline particles of InP, nanocrystalline particles having a core / shell / shell structure, wherein the first shell part is a mixed crystal of ZnS and ZnSe, the second shell part is ZnS, And nanocrystal particles whose core is InP.

  The green light-emitting semiconductor nanocrystal particles include, for example, CdSe nanocrystal particles, mixed crystal nanocrystal particles of CdSe and ZnS, and nanocrystal particles having a core / shell structure, wherein the shell portion is ZnS. And a nanocrystal particle having an inner core portion of InP, a nanocrystal particle having a core / shell structure, wherein the shell portion is a mixed crystal of ZnS and ZnSe and the inner core portion is InP. Nanocrystalline particles having a crystal particle, a core / shell / shell structure, wherein the first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is InP. , A nanocrystal particle having a core / shell / shell structure, wherein a first shell portion is a mixed crystal of ZnS and ZnSe, a second shell portion is ZnS, and an inner core portion. Nanocrystalline particles or the like is InP and the like.

  Examples of the blue light emitting semiconductor nanocrystal particles include ZnSe nanocrystal particles, ZnS nanocrystal particles, and nanocrystal particles having a core / shell structure, wherein the shell portion is ZnSe and the inner core portion is Is a nanocrystal particle of ZnS, a nanocrystal particle of CdS, or a nanocrystal particle having a core / shell structure, wherein the shell portion is ZnS and the inner core portion is InP. Nanocrystalline particles having a structure in which the shell portion is a mixed crystal of ZnS and ZnSe and the inner core portion is InP, and a nanocrystalline particle having a core / shell / shell structure. The first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is InP. And a nanocrystalline, a first shell portion is a mixed crystal of ZnS and ZnSe, a second shell portion is ZnS, include nanocrystalline like core portion of the inner is InP.

  By changing the average particle diameter of the semiconductor nanocrystal particles with the same chemical composition, the color to be emitted from the particles can be changed to red or green. In addition, it is preferable to use semiconductor nanocrystal particles that themselves have as low an adverse effect on the human body as possible. When semiconductor nanocrystal particles containing cadmium, selenium, or the like are used as the luminescent nanocrystal particles, the semiconductor nanocrystal particles containing as little as possible the above elements (cadmium, selenium, etc.) are selected and used alone, or Is preferably used in combination with other luminescent nanocrystal particles so as to minimize as much as possible.

  The shape of the luminescent nanocrystal particles is not particularly limited, and may be any geometric shape or any irregular shape. The shape of the luminescent nanocrystal particles may be, for example, a sphere, an ellipsoid, a pyramid, a disk, a branch, a net, a rod, and the like. However, the use of particles having a small directional shape (eg, spherical, tetrahedral, etc.) as the luminescent nanocrystalline particles can further enhance the uniformity and fluidity of the ink composition. Is preferred.

  The average particle diameter (volume average diameter) of the luminescent nanocrystal particles may be 1 nm or more, from the viewpoint of easily obtaining light emission of a desired wavelength, and from the viewpoint of excellent dispersibility and storage stability, and may be 1.5 nm or more. Or 2 nm or more. From the viewpoint of easily obtaining a desired emission wavelength, the wavelength may be 40 nm or less, 30 nm or less, or 20 nm or less. The average particle diameter (volume average diameter) of the luminescent nanocrystal particles can be obtained by measuring with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.

  The luminescent nanocrystal particles preferably have an organic ligand on the surface from the viewpoint of dispersion stability. The organic ligand may, for example, be coordinated to the surface of the luminescent nanocrystal particle. In other words, the surface of the luminescent nanocrystal particles may be passivated by the organic ligand. When the luminescent ink composition further contains a polymer dispersant described below, the luminescent nanocrystalline particles may have a polymer dispersant on the surface thereof. In the present embodiment, for example, by removing the organic ligand from the luminescent nanocrystal particles having the organic ligand described above, by exchanging the organic ligand and the polymer dispersant, the polymer dispersant on the surface of the luminescent nanocrystal particles May be combined. However, from the viewpoint of dispersion stability when formed into an ink-jet ink, it is preferable that a polymer dispersant is blended with the luminescent nanocrystal particles in which the organic ligand is coordinated.

  As the organic ligand, a functional group for ensuring affinity with a polymerizable compound, an organic solvent, and the like (hereinafter, also simply referred to as “affinity group”) and a functional group capable of binding to the luminescent nanocrystal particles ( A functional group for securing the adsorptivity to the luminescent nanocrystal particles). The affinity group may be a substituted or unsubstituted aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or may have a branched structure. Further, the aliphatic hydrocarbon group may have an unsaturated bond or may not have an unsaturated bond. The substituted aliphatic hydrocarbon may be a group in which some carbon atoms of the aliphatic hydrocarbon group have been substituted with oxygen atoms. The substituted aliphatic hydrocarbon group may include, for example, a (poly) oxyalkylene group. Here, the “(poly) oxyalkylene group” means at least one of an oxyalkylene group and a polyoxyalkylene group in which two or more alkylene groups are connected by an ether bond. Examples of the functional group capable of binding to the luminescent nanocrystal particles include a hydroxyl group, an amino group, a carboxyl group, a thiol group, a phosphoric acid group, a phosphonic acid group, a phosphine group, a phosphine oxide group, and an alkoxysilyl group. Examples of the organic ligand include TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, and hexylphosphonic acid (HPA). , Tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA).

  The organic ligand preferably has a main chain containing a polyoxyalkylene group, and at least one end of the main chain has one or more functional groups capable of binding to the luminescent nanocrystal particles. Examples of the polyoxyalkylene group contained in the main chain include a polyoxyethylene group and a polyoxypropylene group. The main chain has, for example, a substituted or unsubstituted hydrocarbon group other than the polyoxyalkylene group. The functional group is, for example, a group capable of coordinating with a luminescent nanocrystal particle. The functional group may include, for example, a functional group capable of binding to the luminescent nanocrystal particles. Here, the main chain refers to the longest molecular chain constituting the compound. The substituted or unsubstituted hydrocarbon group may have, for example, 1 to 10 carbon atoms. In the substituted hydrocarbon group, a part of carbon atoms may be substituted with a hetero atom such as a sulfur atom or a nitrogen atom, a carbonyl group or the like.

  The organic ligand has at least one first functional group capable of binding to the luminescent nanocrystal particles at one end of the main chain, and a second functional group different from the first functional group at the other end of the main chain. It may have a group. The first functional group may be the same as the group described above as the functional group capable of binding to the luminescent nanocrystal particles. The number of the first functional groups may be one or more, two or more, or two. The second functional group may be the same as the group described above as the functional group capable of binding to the luminescent nanocrystal particles, or may be another group different from the functional group. Other groups may be, for example, a cycloalkyl group or an aryl group. The number of the second functional groups may be one or more, and may be one.

［式（１−１）中、ｐは０〜５０の整数を示し、ｑは０〜５０の整数を示す。］ In one embodiment, the organic ligand may be an organic ligand represented by the following formula (1-1).

[In the formula (1-1), p represents an integer of 0 to 50, and q represents an integer of 0 to 50. ]

  In the organic ligand represented by the formula (1-1), at least one of p and q is preferably 1 or more, and more preferably both p and q are 1 or more.

  In one embodiment, the first functional group is a carboxyl group, the second functional group is a hydroxyl group, and the organic ligand may have two or more first functional groups. That is, in one embodiment, the organic ligand may have one or more carboxyl groups at one end of the main chain, may have a hydroxyl group at the other end of the main chain, and may have a carboxyl group at one end of the main chain. It may have two or more groups and may have a hydroxyl group at the other end of the main chain.

The organic ligand may be, for example, an organic ligand represented by the following formula (1-2).

In Formula (1-2), A ¹ represents a monovalent group containing a carboxyl group, A ² represents a monovalent group containing a hydroxyl group, and R represents a hydrogen atom, a methyl group, or an ethyl group. L represents a substituted or unsubstituted alkylene group, and r represents an integer of 0 or more. The number of carboxyl groups in the monovalent group containing a carboxyl group may be two or more, may be two or more and four or less, or may be two. The alkylene group represented by L may have, for example, 1 to 10 carbon atoms. In the alkylene group represented by L, part of carbon atoms may be substituted with a hetero atom, and at least one hetero atom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom is used. Is also good. r may be, for example, an integer of 1 to 100 or an integer of 10 to 20.

The organic ligand is preferably an organic ligand represented by the following formula (1-2A).

  In the formula (1-2A), r has the same meaning as described above.

  The organic ligand is preferably an organic ligand represented by the formula (1-2A) from the viewpoint of the external quantum efficiency of the luminescent ink composition and the heat resistance of the external quantum efficiency.

  As the luminescent nanocrystal particles, those dispersed in a colloidal form in an organic solvent, a photopolymerizable compound, or the like can be used. The surface of the luminescent nanocrystal particles dispersed in the organic solvent is preferably passivated by the above-mentioned organic ligand. Examples of the organic solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, 1,4-butanediol diacetate, and a mixture thereof. No.

  Commercial products can be used as the luminescent nanocrystal particles. Commercially available luminescent nanocrystal particles include, for example, indium phosphide / zinc sulfide, D-dot, CuInS / ZnS, and InP / ZnS from Aldrich.

  The content of the luminescent nanocrystal particles may be 5% by mass or more and 10% by mass or more based on the mass of the nonvolatile component of the luminescent ink composition from the viewpoint of improving the external quantum efficiency. May be 15% by mass or more, and may be 20% by mass or more. When the content of the luminescent nanocrystal particles is 5% by mass or more, excellent luminescence intensity is obtained, and thus such a luminescent ink composition is suitably used for a color filter. From the same viewpoint, the content of the luminescent nanocrystal particles may be not more than 80% by mass, may be not more than 75% by mass, and may be not more than 70% by mass, based on the mass of the nonvolatile component of the luminescent ink composition. % Or less, or 60% by mass or less. The content of the luminescent nanocrystal particles is 80% by mass or less based on the mass of the nonvolatile components of the luminescent ink composition from the viewpoint of more excellent ejection stability. Further, when the content of the luminescent nanocrystal particles is 80% by mass or less, excellent luminescence intensity is obtained, and thus such a luminescent ink composition is suitably used as an inkjet ink for a color filter. The content of the luminescent nanocrystal particles is 5 to 80% by mass, 10 to 80% by mass, 15 to 80% by mass, 10 to 60% by mass, and 15 to 50% by mass based on the mass of the nonvolatile component of the luminescent ink composition. It may be 60% by weight or 20 to 60% by weight. In addition, in this specification, "the mass of the non-volatile content of the ink composition", when the ink composition contains a solvent, refers to the mass excluding the mass of the solvent from the total mass of the ink composition, the ink composition When no solvent is contained, it refers to the total weight of the ink composition.

  The luminescent ink composition may include, as luminescent nanocrystal particles, two or more of red luminescent nanocrystal particles, green luminescent nanocrystal particles, and blue luminescent nanocrystal particles, but preferably It contains only one of these particles. When the luminescent ink composition includes red luminescent nanocrystal particles, the content of the green luminescent nanocrystal particles and the content of the blue luminescent nanocrystal particles are preferably based on the total mass of the luminescent nanocrystal particles. Is 10% by mass or less, and more preferably 0% by mass. When the luminescent ink composition includes green luminescent nanocrystal particles, the content of the red luminescent nanocrystal particles and the content of the blue luminescent nanocrystal particles are preferably based on the total mass of the luminescent nanocrystal particles. Is 10% by mass or less, and more preferably 0% by mass.

[Photopolymerizable compound]
The photopolymerizable compound of the present embodiment is a compound that is polymerized by light irradiation, and is, for example, a photoradical polymerizable compound or a cationic photopolymerizable compound. The photopolymerizable compound may be a photopolymerizable monomer or oligomer. These are used together with a photopolymerization initiator. The radical photopolymerizable compound is used together with a radical photopolymerization initiator, and the cationic photopolymerizable compound is used together with a cationic photopolymerization initiator. In other words, the luminescent ink composition may contain a photopolymerizable component including a photopolymerizable compound and a photopolymerization initiator, and may include a photoradical polymerizable component including a photoradical polymerizable compound and a photoradical polymerization initiator. Or a cationic photopolymerizable component including a cationic photopolymerizable compound and a cationic photopolymerization initiator. A photo-radical polymerizable compound and a photo-cationic polymerizable compound may be used in combination, and a compound having photo-radical polymerizable and photo-cationic polymerizable properties may be used. May be used in combination. One photopolymerizable compound may be used alone, or two or more photopolymerizable compounds may be used in combination.

  Examples of the photo-radical polymerizable compound include a monomer having an ethylenically unsaturated group (hereinafter, also referred to as “ethylenically unsaturated monomer”), a monomer having an isocyanate group, and the like. Here, the ethylenically unsaturated monomer means a monomer having an ethylenically unsaturated bond (carbon-carbon double bond). Examples of the ethylenically unsaturated monomer include a monomer having an ethylenically unsaturated group such as a vinyl group, a vinylene group, and a vinylidene group. Monomers having these groups may be referred to as "vinyl monomers."

  The number of ethylenically unsaturated bonds (for example, the number of ethylenically unsaturated groups) in the ethylenically unsaturated monomer is, for example, 1 to 3. One kind of the ethylenically unsaturated monomer may be used alone, or two or more kinds may be used in combination. The photopolymerizable compound has one or two ethylenically unsaturated groups from the viewpoint of easily achieving both excellent ejection stability and excellent curability, and from the viewpoint of further improving external quantum efficiency. It may include a monomer and a monomer having two or three ethylenically unsaturated groups. That is, the ethylenically unsaturated monomer is a monofunctional monomer and a bifunctional monomer, a monofunctional monomer and a trifunctional monomer, a difunctional monomer and a difunctional monomer, and at least selected from the group consisting of a difunctional monomer and a trifunctional monomer. One combination may be included. In this embodiment, the photopolymerizable compound preferably contains two or more monomers having two ethylenically unsaturated bonds.

  Examples of the ethylenically unsaturated group include a vinyl group, a vinylene group, a vinylidene group, and a (meth) acryloyl group. In this specification, “(meth) acryloyl group” means “acryloyl group” and the corresponding “methacryloyl group”. The same applies to the expressions “(meth) acrylate” and “(meth) acrylamide”.

  As the ethylenically unsaturated monomer, a (meth) acrylate monomer having a (meth) acryloyl group is preferably used from the viewpoint of more excellent external quantum efficiency. However, it is preferable that the ethylenically unsaturated group is not a (meth) acrylamide group from the viewpoint of easily improving the ejection stability. That is, the monomer having an ethylenically unsaturated group preferably does not include a monomer having a (meth) acrylamide group.

  The ethylenically unsaturated group contained in the ethylenically unsaturated monomer is preferably not a vinyl ether group from the viewpoint of easily improving the ejection stability. That is, the ethylenically unsaturated monomer preferably does not include a monomer having a vinyl ether group. In particular, when the luminescent ink composition contains a compound having a carboxyl group, the viscosity of the luminescent ink composition increases due to the reaction between the carboxyl group and the vinyl ether group, and it becomes difficult to obtain sufficient ejection stability.

  As the monofunctional monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) Acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Ethoxyethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylbenzyl (meth) acrylate, mono (2-acryloyloxyethyl) succinate, N- [2- (acryloyloxy) ethyl] phthalimide, N- [2- (acryloyloxy) ethyl] tetrahydrophthalimide and the like can be mentioned. Among these, ethoxyethoxyethyl (meth) acrylate is preferably used.

  Specific examples of the monomer having two ethylenically unsaturated groups (bifunctional monomer) include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentane Diol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,8-octanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate ) Acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate acrylate, tris (2-hydroxyethyl) isocyanurate Di (meth) acrylate in which hydroxyl groups are substituted by (meth) acryloyloxy groups, and two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol have (meth) Di (meth) acrylate substituted with an acryloyloxy group, and two hydroxyl groups of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, have (meth) acryloyloxy The di (meth) acrylate substituted with a silyl group, and two hydroxyl groups of a triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane were substituted with a (meth) acryloyloxy group. Di (meth) acrylate, di (meth) acrylate in which two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A are substituted with a (meth) acryloyloxy group, and the like. Can be Among these, dipropylene glycol di (meth) acrylate is preferably used.

  Specific examples of the monomer having three ethylenically unsaturated groups (trifunctional monomer) include glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and the like. Among these, glycerin tri (meth) acrylate is preferably used.

  Examples of the cationic photopolymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether compound.

  Examples of the epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolak type epoxy compounds, aliphatic epoxy compounds such as trimethylolpropane polyglycidyl ether and neopentyl glycol diglycidyl ether, and 1,2-epoxy- Alicyclic epoxy compounds such as 4-vinylcyclohexane and 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane;

  It is also possible to use a commercially available product as the epoxy compound. As commercially available epoxy compounds, for example, "Celoxide 2000", "Celoxide 3000", "Celoxide 4000", etc., manufactured by Daicel Chemical Industries, Ltd. can be used.

  Examples of cationically polymerizable oxetane compounds include 2-ethylhexyl oxetane, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl-3. -Normal butyl oxetane, 3-hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl- 3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane , 3-hydroxypropyl-3-phenyl oxetane, 3-hydroxybutyl-3-methyl oxetane, and the like.

  It is also possible to use a commercially available product as the oxetane compound. Commercially available oxetane compounds include, for example, Alon oxetane series manufactured by Toagosei Co., Ltd. (“OXT-101”, “OXT-212”, “OXT-121”, “OXT-221”, etc.); Daicel Chemical Industries, Ltd. "Ceroxide 2021", "Ceroxide 2021A", "Ceroxide 2021P", "Ceroxide 2080", "Ceroxide 2081", "Ceroxide 2083", "Ceroxide 2085", "Epolide GT300", "Epolide GT301", "Epolide" "GT302", "Eporide GT400", "Eporide GT401" and "Eporide GT403"; "Cyracure UVR-6105", "Cyracure UVR-6107", "Cyracure UVR-6" manufactured by Dow Chemical Japan KK 10 "," Cylacure UVR-6128 ", and the like can be used" ERL4289 "and" ERL4299 ". Further, known oxetane compounds (for example, oxetane compounds described in JP-A-2009-40830) can also be used.

  Examples of the vinyl ether compound include 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.

  Further, as the photopolymerizable compound in the present embodiment, the photopolymerizable compounds described in paragraphs 0042 to 0049 of JP2013-182215A can also be used.

  In the light-emitting ink composition of the present embodiment, when the curable component is composed of only a photopolymerizable compound or a main component thereof, the photopolymerizable compound as described above has one polymerizable group. It is more preferable to use, as an essential component, a bifunctional or higher polyfunctional photopolymerizable compound having two or more therein, since the durability (strength, heat resistance, etc.) of the cured product can be further increased.

When the luminescent ink composition of the present embodiment contains at least two different monomers as ethylenically unsaturated monomers, at least two monomers have the following δd, δp, and δh in the Hansen solubility parameter, respectively. It may contain two types of monomers that meet the conditions, and is selected from the group consisting of monofunctional monomers and bifunctional monomers, monofunctional monomers and trifunctional monomers, difunctional monomers and difunctional monomers, and difunctional monomers and trifunctional monomers. At least one combination.
16.0 MPa ^0.5 ≦ δd <18.0 MPa ^0.5
2.5 MPa ^0.5 ≦ δp <5.5 MPa ^0.5
2.5 MPa ^0.5 ≦ δh <8.0 MPa ^0.5

  The Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components, δd, δp, and δh, and expressing it in a three-dimensional space. δd indicates an effect by nonpolar interaction, δp indicates an effect by dipole force, and δh indicates an effect by hydrogen bonding force. Hansen solubility parameter values for various monomers are described, for example, in Charles M. et al. The Hansen solubility parameter values for monomers not described in “Hansen Solubility Parameters: A Users Handbook” by Hansen, etc., can be calculated using computer software (Hansen Solvity Parameters in Practice (HSPiP)). .

  When the luminescent ink composition contains three or more types of ethylenically unsaturated monomers, it is preferable that δd, δp, and δh in the Hansen solubility parameters of all the ethylenically unsaturated monomers satisfy the above conditions. May further contain, as an ethylenically unsaturated monomer, a monomer other than the monomer in which each of δd, δp, and δh in the Hansen solubility parameter satisfies the above conditions.

It is preferable that the two types of monomers constituting the combination are compatible with each other. Specifically, δd (dispersion term), δp (polar term) and δh (hydrogen bond term) in the Hansen solubility parameter (HSP) of one monomer, and δd (hydrogen bond term) in the Hansen solubility parameter (HSP) of the other monomer The dispersion term), δp (polar term) and δh (hydrogen bond term) preferably satisfy the following conditions, respectively.
16.0 MPa ^0.5 ≦ δd <18.0 MPa ^0.5
2.5 MPa ^0.5 ≦ δp <5.5 MPa ^0.5
2.5 MPa ^0.5 ≦ δh <8.0 MPa ^0.5
In other words, at least two types of monomers having an ethylenically unsaturated group are preferably two types of monomers constituting the above-mentioned combination, in which each of δd, δp and δh in the Hansen solubility parameter satisfies the above condition. Including species of monomers. When δd, δp, and δh in the Hansen solubility parameters of the two monomers constituting the above combination satisfy the above conditions, the compatibility between the two monomers becomes good, and the external quantum efficiency tends to be further improved.

  When the monomer having a small number of functional groups (monofunctional monomer or bifunctional monomer) is referred to as monomer A among the two types of monomers constituting the above combination, the monomer A is 2 mPa · s at 23 ° C. from the viewpoint of improving curability. As described above, a monomer having a viscosity of 3 mPa · s or more, 5 mPa · s or more, or 6 mPa · s or more is preferable, and from the viewpoint of easily improving discharge stability, at 23 ° C., 40 mPa · s or less, 6 mPa · s or less, or 4 mPa · s. Monomers having the following viscosities are preferred. When a monomer having a large number of functional groups (a difunctional monomer or a trifunctional monomer) is referred to as a monomer B among the two types of monomers constituting the above combination, the monomer B is 3 mPa from the viewpoint of improving the dispersibility of the light scattering particles. A monomer having a viscosity of at least 5 mPa · s or at least 5 mPa · s or at least 8 mPa · s is preferable, and from the viewpoint of easily improving discharge stability, at most 70 mPa · s, at most 65 mPa · s, at most 40 mPa · s, at most 15 mPa · s. Alternatively, a monomer having a viscosity of 10 mPa · s or less is preferable. That is, it is preferable to combine a monomer A having a viscosity of 2 to 40 mPa · s at 23 ° C. and a monomer B having a viscosity of 3 to 70 mPa · s at 23 ° C., and a viscosity of 2 to 40 mPa · s at 23 ° C. It is more preferable to combine a monomer A having a viscosity of 5 to 65 mPa · s at 23 ° C. When the combination of two types of monomers is a combination of two types of bifunctional monomers, one of the bifunctional monomers may satisfy the viscosity of the monomer A, and the other monomer may satisfy the viscosity of the monomer B. preferable.

  The luminescent ink composition of the present embodiment may include, for example, an alicyclic epoxy compound and an oxetane compound as the photopolymerizable compound, and may include only two types of the alicyclic epoxy compound and the oxetane compound. May be included. In this case, at least one of the alicyclic epoxy compound and the oxetane compound may be monofunctional. That is, the photopolymerizable compound may include an alicyclic epoxy compound having one alicyclic epoxy group as a polymerizable group and / or an oxetane compound having one oxetane group as a polymerizable group. When the luminescent ink composition contains such a photopolymerizable compound, the composition has excellent ejection properties.

  When the alicyclic epoxy compound is monofunctional, the oxetane compound may be monofunctional or bifunctional or more (having two or more oxetane groups), and is preferably monofunctional or bifunctional. . When the oxetane compound is monofunctional, the alicyclic epoxy compound may be monofunctional or bifunctional or more, and is preferably monofunctional or bifunctional. The bifunctional or higher alicyclic epoxy compound has two or more epoxy groups as a polymerizable group, and at least one of the two or more epoxy groups may be an alicyclic epoxy group. That is, for example, a bifunctional alicyclic epoxy compound may have two alicyclic epoxy groups, and may include one alicyclic epoxy group and one epoxy group other than the alicyclic epoxy group. May be provided. From the viewpoint of further improving the curability of the coating film, the photopolymerizable compound preferably includes a combination in which one of the alicyclic epoxy compound and the oxetane compound is monofunctional and the other is bifunctional.

  Examples of monofunctional alicyclic epoxy compounds include 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, and 3-acryloyloxymethylcyclohexene Oxide and 3-vinylcyclohexene oxide. As these monofunctional alicyclic epoxy compounds, commercially available products such as "Celloxide 2000" and "Cyclomer M100" manufactured by Daicel Corporation can be used.

  Examples of the bifunctional alicyclic epoxy compound include limonene diepoxide, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane, 3 ′, 4′-epoxy Cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and the like. Commercial products can also be used as these bifunctional epoxy compounds. Examples of commercially available epoxy compounds include, for example, “CELLOXIDE 2021P” manufactured by Daicel Corporation, “Siracure UVR-6105”, “Siracure UVR-6107”, and “Siracure UVR-6110” manufactured by Dow Chemical Japan, Inc., and "Siracure UVR-6128", "ERL4299" manufactured by Union Carbide, or the like can be used.

  Examples of trifunctional or higher functional alicyclic epoxy compounds include compounds such as tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate-modified ε-caprolactone. As these trifunctional or higher-functional alicyclic epoxy compounds, “Epolide GT300”, “Epolide GT301”, and “Epolide GT302” (both trifunctional), “Epolide GT400”, and “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd. And "Eporide GT403" (above, tetrafunctional), "ERL4289" (trifunctional) manufactured by Union Carbide, and the like.

  As monofunctional oxetane compounds, 2-ethylhexyl oxetane, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3- Normal butyl oxetane, 3-hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3 -Propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3- Droxypropyl-3-phenyloxetane, 3-hydroxybutyl-3-methyloxetane, (3-methyl-3-oxetanyl) methyl methacrylate, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- Oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, and the like. As these monofunctional oxetane compounds, commercially available products such as "OXMA" of Ube Industries, Ltd., "OXT-101", "OXT-211", "OXT-212" and "OXT-213" of Toagosei Co., Ltd. It is possible to use

  Examples of the bifunctional oxetane compound include xylylenebisoxetane, bis [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4,4'-bis [(3-ethyl-3-oxetanylmethoxy) methyl] biphenyl and the like. As these bifunctional oxetane compounds, commercially available products such as “OXT-121” and “OXT-221” manufactured by Toagosei Co., Ltd. can be used.

  Examples of the trifunctional or higher oxetane compound include compounds such as 1,3,3-tris (4- (2- (3-oxetanyl) butoxyphenyl) butane.

  The content of the alicyclic epoxy compound may be 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the mass of the nonvolatile components of the luminescent ink composition. Good. The content of the alicyclic epoxy compound may be 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the mass of the nonvolatile components of the luminescent ink composition. Good.

  The content of the oxetane compound may be 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the mass of the nonvolatile components of the luminescent ink composition. The content of the oxetane compound may be 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the mass of the nonvolatile components of the luminescent ink composition.

  The ratio of the content of the oxetane compound to the content of the alicyclic epoxy compound (oxetane compound / alicyclic epoxy compound) may be 20/80 or more, may be 40/60 or more, and may be 60/40 or more. It may be. The ratio may be 80/20 or less, may be 60/40 or less, or may be 40/60 or less.

  When the photopolymerizable compound includes an alicyclic epoxy compound and an oxetane compound, and at least one of the alicyclic epoxy compound and the oxetane compound is monofunctional, the luminescent ink composition includes a photoacid generator, One or more compounds selected from the group consisting of a sensitizing compound (for example, a photosensitizing compound having a maximum absorption wavelength in a wavelength range of 380 nm or more) and a diol compound (for example, a diol compound having 4 or more carbon atoms); Is preferable.

  Examples of the photosensitizing compound include 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone.

  Examples of the diol compound include 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 1-methyl-1. , 4-butanediol and the like.

  The photopolymerizable compound may be alkali-insoluble from the viewpoint of easily obtaining a highly reliable pixel portion (a cured product of the luminescent ink composition). In the present specification, the term “photopolymerizable compound is alkali-insoluble” means that the amount of the photopolymerizable compound dissolved in a 1% by mass aqueous potassium hydroxide solution at 25 ° C. is 30% based on the total mass of the photopolymerizable compound. % By mass or less. The dissolution amount of the photopolymerizable compound is preferably 10% by mass or less, more preferably 3% by mass or less.

  The content of the photopolymerizable compound is determined from the viewpoint that an appropriate viscosity is easily obtained as an inkjet ink, the viewpoint that the curability of the luminescent ink composition is improved, and the content of the pixel portion (the cured product of the luminescent ink composition). From the viewpoint of improving the solvent resistance and the abrasion resistance, the amount may be 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the mass of the nonvolatile components of the luminescent ink composition. It may be. The content of the photopolymerizable compound is determined from the viewpoint that an appropriate viscosity is easily obtained as an inkjet ink, and from the viewpoint that more excellent optical characteristics (for example, an effect of suppressing a decrease in external quantum efficiency) are obtained. 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass The following may be used.

[Photopolymerization initiator]
As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is suitable.

  Examples of the molecular cleavage type photoradical polymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenyl Phosphine oxide and the like are preferably used. Other than these, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one may be used in combination.

  Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenyl sulfide, and the like. A molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.

  Examples of the cationic photopolymerization initiator include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, and P-nonylphenyliodonium hexafluoroantimonate. And polyaryliodonium salts such as acrylates.

  Commercial products can be used as the cationic photopolymerization initiator. Commercially available products include sulfonium salt-based photocationic polymerization initiators such as "CPI-100P" manufactured by San Apro, acylphosphine oxide compounds such as "Lucirin TPO" manufactured by BASF, "Irgacure 907" manufactured by BASF, “Irgacure 819”, “Irgacure 379EG”, “Irgacure 184”, and “Irgacure PAG290”.

  In the present embodiment, from the viewpoint of obtaining excellent external quantum efficiency, the luminescent ink composition may include a photopolymerization initiator having a molecular weight of 350 or less as the photopolymerization initiator. In particular, when the content of the luminescent nanocrystal particles is 5 to 50% by mass based on the mass of the nonvolatile component of the ink composition, the luminescent ink composition has a photopolymerization initiator having a molecular weight of 350 or less. It is preferable to include

  The molecular weight of the photopolymerization initiator is preferably 330 or less from the viewpoint of improving the external quantum efficiency, and from the viewpoint of easily achieving both ejection stability and curability. The molecular weight of the photopolymerization initiator is preferably 150 or more, more preferably 200 or more, and further preferably 250 or more, from the viewpoint of improving the external quantum efficiency, and from the viewpoint of easily achieving both ejection stability and curability. And more preferably 300 or more. From these viewpoints, the molecular weight of the photopolymerization initiator may be 150 to 350, 200 to 350, 250 to 350, 300 to 350, 150 to 330, 200 to 330, 250 to 330, or 300 to 330. Although the luminescent ink composition may contain a photopolymerization initiator having a molecular weight of more than 350, the content of the photopolymerization initiator having a molecular weight of 350 or less in the total amount of the photopolymerization initiator is preferably 1 % By mass or more, more preferably 2% by mass or more. In the total amount of the photopolymerization initiator, the content of the photopolymerization initiator having a molecular weight of 350 or less may be 50% by mass or more, 70% by mass or more, or 90% by mass or more. The content of the photopolymerization initiator having a molecular weight of 350 or less may be 100% by mass.

  The content of the photopolymerization initiator, from the viewpoint of curability of the luminescent ink composition, may be 0.1 parts by mass or more, based on 100 parts by mass of the photopolymerizable compound, and 0.5 parts by mass or more. And may be 1 part by mass or more. The content of the photopolymerization initiator may be 40 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of the temporal stability of the pixel portion (cured product of the light-emitting ink composition). It may be not more than 20 parts by mass.

[Thermosetting resin]
In the present embodiment, the thermosetting resin is a resin that is crosslinked and cured by heat. The thermosetting resin is, for example, a resin that functions as a binder in a cured product. The thermosetting resin has a curable group. Examples of the curable group include an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxyl group, a methylol group, and the like. From the viewpoint of excellent heat resistance and storage stability of the cured product of the luminescent ink composition, and An epoxy group is preferred from the viewpoint of excellent adhesion to a portion (for example, a black matrix) and a substrate. The thermosetting resin may have one kind of curable group, or may have two or more kinds of curable groups.

  Note that, among the thermosetting resins, a resin having photo-radical polymerizability (polymerizes by irradiation of light when used together with a photo-radical polymerization initiator) and a photo-cationic polymerizable (photo-cationic polymerization) (Polymerized by irradiation with light when used with an initiator). When the luminescent ink composition contains a photo-radical polymerizable thermosetting resin and a photo-radical polymerization initiator, the photo-radical polymerizable thermosetting resin is a photo-radical polymerizable compound (photo-polymerizable compound). ). When the luminescent ink composition contains a photo-cationic polymerizable thermosetting resin and a photo-cationic polymerization initiator, the photo-cationic polymerizable thermosetting resin is a photo-cationic polymerizable compound (photo-polymerizable compound). ).

  The thermosetting resin may be a polymer of a single monomer (homopolymer) or a copolymer of a plurality of types of monomers (copolymer). Further, the thermosetting resin may be any of a random copolymer, a block copolymer, and a graft copolymer.

  As the thermosetting resin, a compound having two or more thermosetting groups in one molecule is used, and is usually used in combination with a curing agent. When a thermosetting resin is used, a catalyst (curing accelerator) capable of accelerating the thermosetting reaction may be further added. In other words, the luminescent ink composition may contain a thermosetting component including a thermosetting resin (and a curing agent and a curing accelerator used as needed). Further, in addition to these, a polymer having no polymerization reactivity itself may be further used.

  As the compound having two or more thermosetting groups in one molecule, for example, an epoxy resin having two or more epoxy groups in one molecule (hereinafter, also referred to as “polyfunctional epoxy resin”) may be used. "Epoxy resin" includes both monomeric and polymeric epoxy resins. The number of epoxy groups in the molecule of the polyfunctional epoxy resin is preferably 2 to 50, and more preferably 2 to 20. The epoxy group only needs to have a structure having an oxirane ring structure, and may be, for example, a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, or the like. Examples of the epoxy resin include known polyvalent epoxy resins that can be cured by a carboxylic acid. Such epoxy resins are widely disclosed, for example, in "Epoxy Resin Handbook" edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (1987), and these can be used.

  Examples of the thermosetting resin having an epoxy group (including a polyfunctional epoxy resin) include a polymer of a monomer having an oxirane ring structure, and a copolymer of a monomer having an oxirane ring structure and another monomer. Specific polyfunctional epoxy resins include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl. Examples include methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate. Further, as the thermosetting resin of the present embodiment, the compounds described in paragraphs 0044 to 0066 of JP-A-2014-56248 can also be used.

  Examples of the polyfunctional epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, and naphthalene epoxy resin. Resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene Phenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin Fat, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

  More specifically, bisphenol A epoxy resin such as "Epicoat 828" (manufactured by Japan Epoxy Resin), bisphenol F epoxy resin such as "YDF-175S" (manufactured by Toto Kasei), trade name Brominated bisphenol A-type epoxy resin such as "YDB-715" (manufactured by Toto Kasei), bisphenol S-type epoxy resin such as "EPICLON EXA1514" (manufactured by DIC), and product name "YDC-1312" (Toto) Hydroquinone type epoxy resins such as "Epiclon EXA4032", "HP-4770", "HP-4700", and "HP-5000" (manufactured by DIC Corporation); "Epicoat YX4000H" (made by Japan Epoxy Resin) Which biphenyl type epoxy resin, bisphenol A type novolak type epoxy resin such as trade name “Epicoat 157S70” (manufactured by Japan Epoxy Resin), trade name “Epicoat 154” (manufactured by Japan Epoxy Resin), trade name “YDPN-638” Phenol novolak type epoxy resin such as (Toto Kasei Co., Ltd.), cresol novolak type epoxy resin such as trade name “YDCN-701” (Toto Kasei Co., Ltd.), trade names “EPICLON HP-7200”, “HP-7200H” ( Dicyclopentadiene phenol type epoxy resin such as DIC Corporation), trishydroxyphenylmethane type epoxy resin such as "Epicoat 1032H60" (manufactured by Japan Epoxy Resin), "VG3101M80" (manufactured by Mitsui Chemicals), etc. Trifunctional epoxy resin, tetraphenylolethane type epoxy resin such as "Epicoat 1031S" (trade name, manufactured by Japan Epoxy Resin), and tetrafunctional epoxy resin such as "Denacol EX-411" (trade name, manufactured by Nagase Kasei Kogyo) Resin, hydrogenated bisphenol A type epoxy resin such as trade name "ST-3000" (manufactured by Toto Kasei), glycidyl ester type epoxy resin such as trade name "Epicoat 190P" (manufactured by Japan Epoxy Resin), trade name "YH" -434 "(manufactured by Toto Kasei), glyoxal type epoxy resin such as" YDG-414 "(manufactured by Toto Kasei), and" Eporid GT-401 "(manufactured by Daicel Chemical) ), Triglycidyl isocyanate (TGIC )) And the like. If necessary, an epoxy-reactive diluent such as "Neo Tote E" (manufactured by Toto Kasei Co., Ltd.) can be mixed.

  Examples of the polyfunctional epoxy resin include “FINEDIC A-247S”, “FINEDIC A-254”, “FINEDIC A-253”, “FINEDIC A-229-30A”, and “FINEDIC A-229-30A” manufactured by DIC Corporation. Dick A-261 "," Fine Dick A249 "," Fine Dick A-266 "," Fine Dick A-241 "," Fine Dick M-8020 "," EPICLON N-740 "," EPICLON N-770 "," EPICLON N-865 "(trade name) or the like can be used.

  When a polyfunctional epoxy resin having a relatively small molecular weight is used as the thermosetting resin, epoxy groups are replenished in the luminescent ink composition (inkjet ink), and the concentration of epoxy reaction points becomes high, increasing the crosslink density. be able to.

  Among polyfunctional epoxy resins, it is preferable to use an epoxy resin having four or more epoxy groups in one molecule (a polyfunctional epoxy resin having four or more functional groups) from the viewpoint of increasing the crosslink density. In particular, when a thermosetting resin having a weight-average molecular weight of 10,000 or less is used in order to improve the ejection stability from the ejection head in the inkjet method, the strength and hardness of the pixel portion (the cured product of the luminescent ink composition) are increased. Therefore, it is preferable to mix a polyfunctional epoxy resin having four or more functional groups into the luminescent ink composition (inkjet ink) from the viewpoint of sufficiently increasing the crosslinking density.

  The epoxy group content of the epoxy resin present in the luminescent ink composition may be 0.0040 mol or less per gram of the luminescent nanocrystal particles, and is preferably 0.0030 mol from the viewpoint of further improving the external quantum efficiency. Hereinafter, it is 0.0020 mol or less, or 0.0010 mol or less. The amount of epoxy group of the epoxy resin present in the luminescent ink composition may be, for example, 0.00010 mol or more, or 0.00030 mol or more per gram of the luminescent nanocrystal particles.

  The epoxy equivalent (g / eq) of the epoxy resin may be 195 or more, 400 or more, or 1000 or more from the viewpoint of improving external quantum efficiency, and from the viewpoint of improving curability and improving film strength, It may be 4000 or less. The epoxy equivalent can be measured according to the method described in JIS K7236: 2001.

  The thermosetting resin is, for example, a polymer of an epoxy group-containing acrylic monomer having an epoxy group and a substituted or unsubstituted acryloyl group (for example, an acryloyl group, an α-alkylacryloyl group), and an epoxy group-containing acrylic monomer. When an epoxy group-containing acrylic polymer such as a copolymer with another monomer (a monomer other than the epoxy group-containing acrylic monomer) is included, the epoxy equivalent of the epoxy group-containing acrylic polymer is less than 560 g / eq. May be. When the pixel portion is formed with the luminescent ink composition using the luminescent nanocrystal particles, depending on the type of the epoxy group-containing acrylic polymer, the luminescent ink composition may be stored at room temperature under an air atmosphere at an external temperature. The quantum efficiency may decrease. On the other hand, when the epoxy equivalent of the epoxy group-containing acrylic polymer is less than 560 g / eq, there is a tendency that such a decrease in external quantum efficiency can be suppressed. Further, the thermosetting resin is, for example, a polymer of an epoxy group-containing acrylic monomer having an epoxy group and a substituted or unsubstituted acryloyl group (for example, an acryloyl group or an α-alkylacryloyl group); When an epoxy group-containing acrylic polymer such as a copolymer of a monomer and another monomer (a monomer other than the epoxy group-containing acrylic monomer) is included, a phenol-based curing agent described later is preferably used as the curing agent.

[Curing agent]
Examples of the curing agent used to cure the thermosetting resin include acid anhydrides, phenolic compounds, and amine compounds. These curing agents may be used alone or in combination of two or more. The curing agent preferably contains at least one selected from the group consisting of acid anhydrides, phenolic compounds and amine compounds. When an epoxy resin is used as the thermosetting resin, self-polymerization may be performed using onium salts, organometallic complexes, tertiary amines, imidazoles, or the like.

  Examples of the acid anhydride (acid anhydride-based curing agent) include 4-methylcyclohexane-1,2-dicarboxylic anhydride (4M-HHPA), 3-methylcyclohexane-1,2-dicarboxylic anhydride, and cyclohexane-1. , 2-Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6- Tetrahydrophthalic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methyl-3,6 end Methylene-1,2,3,6-tetrahydrophthalic anhydride, 3,6 endomethylene-1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, pyrome anhydride Litic acid, maleic anhydride and the like can be mentioned.

  Examples of the phenolic compound (phenolic curing agent) include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4 ', 4 "-trihydroxytriphenylmethane. , Naphthalene diol, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, calixarene, novolak type phenol resin (for example, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, bisphenol S novolak resin, resorcinol Polyphenol phenol novolak resin synthesized from polyhydroxy compound represented by novolak resin and formaldehyde, naphthol-phenol co-condensed novolak resin, naphthol Cresol co-condensed novolak resin, naphthol novolak resin, alkoxy group-containing aromatic ring-modified novolak resin (polyphenol compound in which phenol nucleus and alkoxy group-containing aromatic ring are linked by formaldehyde), aralkyl-type phenol resin (for example, Xyloc) Resins such as phenol aralkyl resins and naphthol aralkyl resins), aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resin, trimethylol methane resin, tetraphenylol ethane resin, and biphenyl-modified phenol resin (phenol with bismethylene group) A polyphenol compound having a nucleus linked thereto), a biphenyl-modified naphthol resin (a polyvalent naphthol compound having a phenol nucleus linked by a bismethylene group), Polyphenol compounds such as modified phenol resins (polyphenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.), etc. From the viewpoint of excellent effect of improving external quantum efficiency, phenol compounds are novolak phenols As the novolak phenol resin, phenol novolak resin, cresol novolak resin and bisphenol A novolak resin are preferably used.

  Specific examples of the novolak type phenolic resin include “PHENOLITE TD-2131” and “PHENOLITE TD-2090” (trade name) manufactured by DIC Corporation, and “GPH-65” and “GPH-103” manufactured by Nippon Kayaku Co., Ltd. (Trade name).

  Examples of the amine-based compound (amine-based curing agent) include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, metaxylylenediamine, diaminodiphenylmethane, and the like. Aromatic polyamines such as phenylenediamine, alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, etc., polyamides synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine Resins.

  From the viewpoint of the heat resistance of the external quantum efficiency of the cured product of the luminescent ink composition, the curing agent is preferably an acid anhydride-based curing agent, and the curability of the cured product of the luminescent ink composition and the luminescent ink composition From the viewpoint of viscosity stability, a phenolic curing agent is desirable.

  The content of the curing agent may be, for example, 40% by mass or less, 30% by mass or less, or 20% by mass or less, based on the mass of the nonvolatile components of the luminescent ink composition. Good.

[Curing accelerator (curing catalyst)]
Examples of the curing accelerator (curing catalyst) used for curing the thermosetting resin include a phosphorus compound, a tertiary amine compound, an imidazole compound, an organic acid metal salt, a Lewis acid, and an amine complex salt. . Examples of the phosphorus compound include triphenylphosphine, triparatolylphosphine, and diphenylcyclohexylphosphine. Examples of the tertiary amine compound include N, N-dimethylbenzylamine, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5, tris (Dimethylaminomethyl) phenol. Examples of the imidazole compound include 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole.

  The thermosetting resin may be alkali-insoluble from the viewpoint of easily obtaining a highly reliable pixel portion (a cured product of the luminescent ink composition). When the thermosetting resin is alkali-insoluble, the amount of the thermosetting resin dissolved in a 1% by mass aqueous potassium hydroxide solution at 25 ° C. is 30% by mass or less based on the total mass of the thermosetting resin. Means that. The amount of the thermosetting resin dissolved is preferably 10% by mass or less, more preferably 3% by mass or less.

  The weight-average molecular weight of the thermosetting resin is such that an appropriate viscosity is easily obtained as an inkjet ink, that the curability of the luminescent ink composition is good, and that the pixel portion (a cured product of the luminescent ink composition) From the viewpoint of improving the solvent resistance and abrasion resistance of the resin, it may be at least 750, at least 1,000, or at least 2,000. From the viewpoint of obtaining an appropriate viscosity as the inkjet ink, the viscosity may be 500,000 or less, 300,000 or less, or 200,000 or less. However, the molecular weight after crosslinking is not limited to this. In addition, in this specification, a weight average molecular weight is a polystyrene conversion weight average molecular weight measured by GPC (gel permeation chromatography, Gel Permeation Chromatography).

  The content of the thermosetting resin is determined from the viewpoint that an appropriate viscosity is easily obtained as an inkjet ink, the viewpoint that the curability of the luminescent ink composition is improved, and the content of the pixel portion (cured product of the luminescent ink composition). From the viewpoint of improving the solvent resistance and abrasion resistance, the amount may be 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the mass of the nonvolatile component of the luminescent ink composition. There may be. The content of the thermosetting resin is based on the mass of the nonvolatile component of the luminescent ink composition from the viewpoint that the viscosity of the inkjet ink does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function. 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less .

  In the present embodiment, the luminescent ink composition only needs to contain at least one of the photopolymerizable compound and the thermosetting resin, and contains both the photopolymerizable compound and the thermosetting resin. Is also good. When the luminescent ink composition contains a photopolymerizable compound, it does not need to contain a thermosetting resin. When the luminescent ink composition contains a thermosetting resin, it does not need to contain a photopolymerizable compound. From the viewpoint of storage stability of a luminescent ink composition containing luminescent nanocrystalline particles (for example, quantum dots) and durability (wet heat stability and the like) of a pixel portion (a cured product of the luminescent ink composition), Of the photopolymerizable compound and the thermosetting resin, it is preferable to use a thermosetting resin, and the storage stability of a luminescent ink composition containing luminescent nanocrystalline particles (for example, quantum dots) and heating of the quantum dots It is more preferable to use a photo-radical polymerizable compound from the viewpoint of being able to cure at a low temperature which is less susceptible to deterioration due to deterioration, and the pixel portion (cured product of the luminescent ink composition) can be formed without being inhibited by oxygen in the curing process. From the viewpoint of formation, it is preferable to use a photocationically polymerizable compound.

  When the luminescent ink composition contains a photopolymerizable compound and a thermosetting resin, the total content of the photopolymerizable compound and the thermosetting resin is preferably such that a proper viscosity is easily obtained as an inkjet ink. In terms of improving the curability of the composition and improving the solvent resistance and abrasion of the pixel portion (cured product of the luminescent ink composition), the mass of the nonvolatile component of the luminescent ink composition is referred to. 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more . In addition, the sum of the content of the photopolymerizable compound and the thermosetting resin is such that the viscosity of the inkjet ink does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function. It may be 80% by mass or less, 60% by mass or less, or 50% by mass or less based on the mass of the non-volatile content of the composition.

  The luminescent ink composition may further contain other components other than the above-described components as long as the effects of the present invention are not impaired. Other components include, for example, light scattering particles, polymer dispersants, solvents, phosphite triester compounds, thiol compounds, and the like.

[Light scattering particles]
The light scattering particles are, for example, optically inactive inorganic fine particles. When the light-emitting ink composition contains light-scattering particles, light from a light source applied to the pixel portion can be scattered, so that excellent optical characteristics can be obtained.

  As a material constituting the light scattering particles, for example, a single metal such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; silica, barium sulfate, barium carbonate, calcium carbonate, Metal oxides such as talc, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, zinc oxide; magnesium carbonate, barium carbonate, Metal carbonates such as bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate; bismuth subnitrate Etc. metal And the like. The light-scattering particles are selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, barium titanate and silica, from the viewpoint of excellent ejection stability and the effect of improving external quantum efficiency. Preferably, at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide and barium titanate is contained.

  The shape of the light-scattering particles may be spherical, filamentous, irregular, or the like. However, as the light-scattering particles, it is preferable to use particles having a small directional shape (for example, particles having a spherical shape, tetrahedral shape, or the like) as the particle shape, so that the uniformity, fluidity, and light scattering property of the ink composition are improved. This is preferable in that it can enhance the discharge stability.

  The light scattering particles may have at least a part of the surface covered with alumina. For example, 50% by area or more of the surface of the light-scattering particles may be covered with alumina, and the entire surface of the light-scattering particles may be covered with alumina. In this case, the light scattering particles can be rephrased as light scattering particles surface-treated with alumina.

  As a method of covering at least a part of the surface of the light-scattering particles with alumina (surface treatment with alumina), for example, a wet treatment method (adding an aluminum salt aqueous solution to the light-scattering particle slurry to neutralize the solution) For adsorbing to the surface of the light-scattering particles). As the light scattering particles, for example, “MPT-141”, “CR-50”, “CR-50-2”, “CR-58”, “CR-58-2”, “CR -60 "," CR-60-2 "," MT-700B "," JR-405 "," JR-603 "," JR-605 "," JR-701 "," JR-701 "manufactured by Teica Corporation. Commercially available products such as "805" and "JR-806" can also be used. The surface of the light-scattering particles may be covered with alumina and other components such as silica, zinc oxide, titanium oxide, zirconium oxide, and organic substances such as stearic acid and polysiloxane.

  The average particle diameter (volume average diameter) of the light-scattering particles in the luminescent ink composition is 0.05 μm (50 nm) or more from the viewpoint of excellent ejection stability and the effect of improving external quantum efficiency. And may be 0.2 μm (200 nm) or more, or 0.3 μm (300 nm) or more. The average particle diameter (volume average diameter) of the light-scattering particles in the luminescent ink composition may be 1.0 μm (1000 nm) or less, or 0.6 μm (600 nm), from the viewpoint of excellent ejection stability. Or less, or 0.4 μm (400 nm) or less. The average particle diameter (volume average diameter) of the light scattering particles in the luminescent ink composition is 0.05 to 1.0 μm, 0.05 to 0.6 μm, 0.05 to 0.4 μm, 0.2 ~ 1.0 μm, 0.2-0.6 μm, 0.2-0.4 μm, 0.3-1.0 μm, 0.3-0.6 μm, or 0.3-0.4 μm . From the viewpoint of easily obtaining such an average particle diameter (volume average diameter), the average particle diameter (volume average diameter) of the light-scattering particles used may be 0.05 μm or more and 1.0 μm or less. May be. In the present specification, the average particle diameter (volume average diameter) of the light scattering particles in the ink composition is obtained by measuring with a dynamic light scattering type nanotrack particle size distribution meter and calculating the volume average diameter. . The average particle diameter (volume average diameter) of the light-scattering particles to be used is obtained by measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope, for example, and calculating the volume average diameter.

  The content of the light-scattering particles in the luminescent ink composition may be 0.1% by mass or more based on the mass of the nonvolatile component of the luminescent ink composition, from the viewpoint of being more excellent in the effect of improving the external quantum efficiency. 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more . The content of the light-scattering particles may be 60% by mass or less, based on the mass of the nonvolatile component of the luminescent ink composition, from the viewpoint of excellent ejection stability and the effect of improving the external quantum efficiency. 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, It may be 15% by mass or less. When the luminescent ink composition contains a polymer dispersant, the light scattering particles are satisfactorily dispersed even when the content of the light scattering particles is relatively large (for example, about 60% by mass). be able to.

  The mass ratio of the content of the light-scattering particles to the content of the light-emitting nanocrystal particles (light-scattering particles / light-emitting nanocrystal particles) is 0.1 or more from the viewpoint of excellent effect of improving the external quantum efficiency. And may be 0.2 or more, or 0.5 or more. The mass ratio (light scattering particles / luminescent nanocrystal particles) may be 5.0 or less from the viewpoint of excellent external quantum efficiency improving effect and excellent continuous dischargeability (discharge stability) during inkjet printing. , 2.0 or less, or 1.5 or less.

[Polymer dispersant]
The polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an affinity for the light scattering particles. The polymer dispersant has a function of dispersing the light scattering particles. The polymer dispersant is adsorbed on the light-scattering particles via a functional group having an affinity for the light-scattering particles, and the light-scattering particles are formed by electrostatic repulsion and / or steric repulsion between the polymer dispersants. It is dispersed in the luminescent ink composition. The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but is preferably bonded to the surface of the light-emitting nanocrystal particles and adsorbed to the light-emitting nanoparticles. And may be released in the luminescent ink composition.

  By the way, aggregation of light-emitting nanocrystal particles and light-scattering particles can be considered as one of the causes of a decrease in ejection stability when a pixel portion is formed by an inkjet method using a conventional ink composition. Therefore, it is conceivable to improve the ejection stability by reducing the content of the luminescent nanocrystal particles and the light scattering particles, reducing the content of the luminescent nanocrystal particles and the light scattering particles, and the like. In this case, the effect of improving the external quantum efficiency tends to decrease, and it is difficult to achieve both excellent ejection stability and excellent external quantum efficiency. On the other hand, according to the luminescent ink composition further containing the polymer dispersant, it is possible to achieve both excellent ejection stability and excellent external quantum efficiency. The reason why such an effect is obtained is not clear, but is because the aggregation of the luminescent nanocrystal particles and the light-scattering particles (particularly, the light-scattering particles) is significantly suppressed by the polymer dispersant. It is inferred.

  Examples of the functional group having an affinity for the light scattering particles include an acidic functional group, a basic functional group, and a nonionic functional group. The acidic functional group has a dissociable proton, and may be neutralized with a base such as an amine or a hydroxide ion.The basic functional group is neutralized with an acid such as an organic acid or an inorganic acid. May be.

Examples of the acidic functional group include a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a sulfate group (—OSO ₃ H), a phosphonic acid group (—PO (OH) ₃ ), and a phosphate group (—OPO ( OH) ₃ ), a phosphinic acid group (—PO (OH) —), and a mercapto group (—SH).

  Examples of the basic functional group include primary, secondary, and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.

The nonionic functional group, hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group _(-SO 2 -), a carbonyl group, a formyl group, an ester group, carbonic ester group, an amide group, Examples include carbamoyl, ureido, thioamide, thioureido, sulfamoyl, cyano, alkenyl, alkynyl, phosphine oxide, and phosphine sulfide groups.

  From the viewpoint of dispersion stability of the light scattering particles, the viewpoint that the side effect that the luminescent nanocrystal particles settle is less likely to occur, the viewpoint of the ease of synthesizing the polymer dispersant, and the viewpoint of the stability of the functional groups, As the group, a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group are preferably used, and as the basic functional group, an amino group is preferably used. Among these, a carboxyl group, a phosphonic acid group and an amino group are more preferably used, and an amino group is most preferably used.

  A polymer dispersant having an acidic functional group has an acid value. The acid value of the polymer dispersant having an acidic functional group is preferably from 1 to 150 mgKOH / g. When the acid value is 1 mgKOH / g or more, sufficient dispersibility of the light-scattering particles is easily obtained, and when the acid value is 150 mgKOH / g or less, storage of the pixel portion (cured product of the luminescent ink composition) is performed. Stability is not easily reduced. The acid value of the polymer dispersant is preferably 50 mgKOH / g or less, more preferably 45 mgKOH / g or less, still more preferably 35 mgKOH / g or less, particularly preferably 30 mgKOH / g or less, particularly preferably 24 mgKOH / g or less.

The acid value of the polymer dispersant was determined by preparing a sample solution in which pg of the polymer dispersant was dissolved in 50 mL of a mixed solution obtained by mixing toluene and ethanol at a volume ratio of 1: 1 and 1 mL of a phenolphthalein test solution. Titrate with a 1 mol / L ethanol-made potassium hydroxide solution (a solution prepared by dissolving 7.0 g of potassium hydroxide in 5.0 mL of distilled water and adjusting to 1000 mL by adding 95 vol% ethanol) until the sample solution becomes pale red. I do. Then, the acid value can be calculated by the following equation.
Acid value = q × r × 5.611 / p
In the formula, q indicates the titer (mL) of the 0.1 mol / L ethanol potassium hydroxide solution required for titration, and r indicates the titer of the 0.1 mol / L ethanol potassium hydroxide solution required for titration. And p represents the mass (g) of the polymer dispersant.

  The polymer dispersant having a basic functional group has an amine value. The amine value of the polymer dispersant having a basic functional group is preferably from 1 to 200 mgKOH / g. When the amine value is 1 mgKOH / g or more, sufficient dispersibility of the light-scattering particles is easily obtained, and when the amine value is 200 mgKOH / g or less, the pixel portion (cured product of the luminescent ink composition) is stored. Stability is not easily reduced. The amine value of the polymer dispersant is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. The amine value of the polymer dispersant is preferably 90 mgKOH / g or less, more preferably 50 mgKOH / g or less.

The amine value of the polymer dispersant was determined by preparing a sample solution in which xg of the polymer dispersant was dissolved in 50 ml of a mixed solution of toluene and ethanol at a volume ratio of 1: 1 and 1 ml of a bromophenol blue test solution. Titration is performed with 5 mol / L hydrochloric acid until the sample solution turns green. Then, the amine value can be calculated by the following equation.
Amine value = y / x × 28.05
In the formula, y indicates the titer (ml) of 0.5 mol / L hydrochloric acid required for the titration, and x indicates the mass (g) of the polymer dispersant.

  The polymer dispersant may be a polymer of a single monomer (homopolymer) or a copolymer of a plurality of types of monomers (copolymer). Further, the polymer dispersant may be any of a random copolymer, a block copolymer, and a graft copolymer. When the polymer dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. The polymer dispersant is, for example, an acrylic resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyether, a phenol resin, a silicone resin, a polyurea resin, an amino resin, an epoxy resin, a polyamine such as polyethyleneimine and polyallylamine, and a polyimide. May be.

  Commercially available products may be used as the polymer dispersant. Examples of the commercially available products include Ajisper PB Series manufactured by Ajinomoto Fine Techno Co., DISPERBYK Series and BYK-Series manufactured by BYK, and Efka Series manufactured by BASF. Etc. can be used.

  Commercially available products include, for example, “DISPERBYK-130”, “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-163”, “DISPERBYK-164”, “DISPERBYK-166”, “DISPERBYK-166” manufactured by Big Chemie. 167 "," DISPERBYK-168 "," DISPERBYK-170 "," DISPERBYK-171 "," DISPERBYK-174 "," DISPERBYK-180 "," DISPERBYK-182 "," DISPERBYK-183 "," DISPERBYK-184 " , “DISPERBYK-185”, “DISPERBYK-2000”, “DISPERBYK-2001”, “DISPERBYK-2008”, “DISP "RBYK-2009", "DISPERBYK-2020", "DISPERBYK-2022", "DISPERBYK-2025", "DISPERBYK-2050", "DISPERBYK-2070", "DISPERBYK-2096", "DISPERBYK-2150", "-DISPERY" 2155 "," DISPERBYK-2163 "," DISPERBYK-2164 "," BYK-LPN21116 "and" BYK-LPN6919 ";" EFKA4010 "," EFKA4015 "," EFKA4046 "," EFKA4047 "," EFKA406 "manufactured by BASF. , “EFKA4080”, “EFKA4300”, “EFKA4310”, “EFKA4320”, “EFKA4330”, “EFK 4340 "," EFKA4560 "," EFKA4585 "," EFKA5207 "," EFKA1501 "," EFKA1502 "," EFKA1503 "and" EFKA PX-4701 ";" SOLSPERS 3000 "," SOLSPERS 9000 ", and" SOLSPERS 9000 ", manufactured by Lubrizol. "SOLSPERS13240", "SOLSPERS13650", "SOLSPERS13940", "SOLSPERS11200", "SOLSPERS13940", "SOLSPERS16000", "SOLSPERS17000", "SOLSPERS18000", "SOLSPERS20000", "SOLSPERS21000", "SOLSPERS21000", Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000 "SOLSPARSE 32500", "SOLSPERS32550", "SOLSPERS32600", "SOLSPERS33000", "SOLSPERS34750", "SOLSPERS35100", "SOLSPERS35200", "SOLSPERS36000", "SOLSPERS37500", "SOLSPERS38500", "SOLSPERS 39000", "SOLSPERS41000", "SOLSPERS54000", "SOLSPERS71000" and "SOLSPERS76500"; "AJISPER PB821", "AZIPPER PB822", "AZIPPER PB881", "PN411" manufactured by Ajinomoto Fine Techno Co., Ltd. And “PA111”; “TEGO Dispers 650”, “TEGO Dispers 660C”, “TEGO” manufactured by Evonik "Dispars 662C", "TEGO Dispers 670", "TEGO Dispers 685", "TEGO Dispers 700", "TEGO Dispers 710" and "TEGO Dispers 760W"; "DISPARON DA-703-DA-503-DA-703-50" manufactured by Kusumoto Kasei 725 "can be used.

  Examples of the polymer dispersant include, besides the above-mentioned commercially available products, a cationic monomer having a basic group and / or an anionic monomer having an acidic group, a monomer having a hydrophobic group, and if necessary, other monomers. (A nonionic monomer, a monomer having a hydrophilic group, etc.) can be used. As for the details of the cationic monomer, the anionic monomer, the monomer having a hydrophobic group, and other monomers, the monomers described in paragraphs 0034 to 0036 of JP-A-2004-250502 can be exemplified.

  Further, for example, compounds obtained by reacting a polyalkyleneimine with a polyester compound described in JP-A-54-37082 and JP-A-61-174939, and polyallylamine described in JP-A-9-169821. Compounds in which the amino group of the side chain is modified with a polyester, graft polymers having a polyester-type macromonomer as a copolymer component described in JP-A-9-171253, and polyester polyol addition described in JP-A-60-166318 Polyurethane and the like are preferred.

  The weight-average molecular weight of the polymer dispersant may be 1,000 or more, from the viewpoint that the light-scattering particles can be dispersed well and the effect of improving the external quantum efficiency can be further improved. Or 3000 or more. The weight average molecular weight of the polymer dispersant can disperse the light-scattering particles favorably, further improve the external quantum efficiency, and discharge the ink-jet ink with stable viscosity. From the viewpoint of obtaining a suitable viscosity, the viscosity may be 100,000 or less, 50,000 or less, or 30,000 or less.

  From the viewpoint of the dispersibility of the light-scattering particles, the content of the polymer dispersant may be 0.5 parts by mass or more with respect to 100 parts by mass of the light-scattering particles, and may be 2 parts by mass or more. The amount may be 5 parts by mass or more. The content of the polymer dispersion may be 50 parts by mass or less with respect to 100 parts by mass of the light-scattering particles, from the viewpoint of wet heat stability of the pixel portion (cured product of the luminescent ink composition), Part or less, or 10 parts by mass or less.

[solvent]
Examples of the solvent include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, and diethyl succinate. , 1,4-butanediol diacetate, glyceryl triacetate and the like.

  The boiling point of the solvent is preferably 150 ° C. or higher, and more preferably 180 ° C. or higher, from the viewpoint of the continuous ejection stability of the inkjet ink. Further, at the time of forming the pixel portion, since it is necessary to remove the solvent from the luminescent ink composition before curing the luminescent ink composition, from the viewpoint of easy removal of the solvent, the boiling point of the solvent is preferably 300 ℃ or less. is there.

  The solvent preferably contains an acetate compound having a boiling point of 150 ° C. or higher. In this case, the affinity between the luminescent nanocrystal particles and the solvent is improved, and the luminescent nanocrystal particles can exhibit excellent luminescent characteristics. Specific examples of the acetate compound having a boiling point of 150 ° C. or more include monoacetate compounds such as diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate, and 1,4-butanediol diacetate. Examples thereof include diacetate compounds such as acetate and propylene glycol diacetate, and triacetate compounds such as glyceryl triacetate.

  In the case of using a thermosetting resin and not using a photopolymerizable compound, the viewpoint of preparing the luminescent ink composition to be uniform, and increasing the fluidity of the luminescent ink composition and the like to reduce unevenness of the pixel portion From the viewpoint of forming the (light conversion layer), it is preferable to use a solvent. On the other hand, when a photopolymerizable compound is used, it becomes possible to disperse the light-scattering particles and the luminescent nanocrystal particles in the photopolymerizable compound without using a solvent. In this case, there is an advantage that a step of removing the solvent by drying when forming the pixel portion is unnecessary.

[Phosphite triester compound]
The phosphite triester compound may be a compound represented by the following formula (2).

In the formula (2), R ¹ , R ² and R ³ each independently represent a monovalent organic group. Two kinds selected from R ¹ , R ² and R ³ may be bonded to each other to form a ring.

  Specific examples of the compound represented by the formula (2) include triphenyl phosphite (triphenyl phosphite), 2-ethylhexyl diphenyl phosphite, diphenyl octyl phosphite, and the like.

  The content of the phosphite triester compound may be 0.01% by mass or more from the viewpoint that the decrease in the fluorescence quantum yield of the inkjet ink is more suppressed, based on the mass of the nonvolatile components of the inkjet ink. , 0.1% by mass or more, 1% by mass or more, or 5% by mass or more. Since a decrease in the fluorescence quantum yield can be more effectively suppressed even by adding a small amount, the content of the phosphite triester compound is preferably 10% by mass or less, based on the mass of the nonvolatile components of the inkjet ink. And more preferably 7% by mass or less, further preferably 5% by mass or less, and still more preferably 3% by mass or less. When the content of the phosphite triester compound is within the above range, at the time of forming the coating film, in addition to being able to ensure better film strength, bleeding to the surface of the phosphite triester compound is more likely. Suppressed and good optical characteristics can be secured.

  When the inkjet ink contains a photopolymerizable compound, the content of the phosphite triester compound is set to 100 parts by mass of the photopolymerizable compound from the viewpoint that a decrease in the fluorescence quantum yield of the inkjet ink is further suppressed. On the other hand, it may be 0.01 part by mass or more, may be 0.1 part by mass or more, may be 0.5 part by mass or more, may be 1 part by mass or more, or may be 3 parts by mass. Parts or more. Since the lowering of the fluorescence quantum yield can be suppressed more effectively even by adding a small amount, the content of the phosphite triester compound is 10 parts by mass or less based on 100 parts by mass of the photopolymerizable compound. It may be 7 parts by mass or less, or 5 parts by mass or less. When the content of the phosphite triester compound is within the above range, in addition to being able to ensure better film strength at the time of forming the coating film, bleeding to the surface of the phosphite triester compound is improved. It tends to be able to suppress and secure good optical characteristics.

  The phosphite triester compound may be liquid or solid at room temperature (25 ° C.), but is preferably compatible with other components (such as a photopolymerizable compound) in the inkjet ink. It is a liquid at room temperature (25 ° C.) from the viewpoint that it sufficiently satisfies the performance requirements of the inkjet ink and can further suppress the decrease in the fluorescence quantum yield of the inkjet ink. The melting point of the phosphite triester compound may be 20 ° C. or lower, or 10 ° C. or lower.

[Thiol compound]
The thiol compound is suitably used when the ink composition contains an ethylenically unsaturated monomer as a photopolymerizable compound. The thiol compound has, for example, two or three primary mercapto groups in one molecule. A primary mercapto group means a mercapto group bonded to a primary carbon atom. That is, the thiol compound has —CH ₂ —SH as a partial structure. The number of primary mercapto groups in the thiol compound is 2 or 3, and preferably 3 from the viewpoint of ejection stability.

  When the thiol compound has a primary mercapto group, when the luminescent ink composition is cured by irradiation with an active energy ray (for example, ultraviolet light), for example, a secondary or tertiary mercapto group (secondary) Alternatively, as compared with a thiol compound having a tertiary carbon atom (mercapto group), curing can be performed with a smaller exposure dose (irradiation dose), and a decrease in external quantum efficiency is easily suppressed.

  Examples of the thiol compound having three primary mercapto groups include trimethylolpropane tris (3-mercaptopropionate). Examples of the thiol compound having two primary mercapto groups include tetraethylene glycol bis (3-mercaptopropionate). The thiol compounds may be used alone or in combination of two or more.

  Commercial products can also be used for the thiol compound. Examples of commercially available thiol compounds having three primary mercapto groups include “TMMP” (trade name) and “PEPT” (trade name) manufactured by SC Organic Chemical Co., Ltd. As a commercially available thiol compound having two primary mercapto groups, “EGMP-4” (trade name) manufactured by SC Organic Chemical Co., Ltd. can be mentioned.

  The content of the thiol compound is 1.0 part by mass or more with respect to 100 parts by mass of the ethylenically unsaturated monomer, from the viewpoint that the ejection stability is further improved and the decrease in external quantum efficiency is further suppressed. The amount may be 8.0 parts by mass or more, or 14.0 parts by mass or more. The content of the thiol compound may be 32.5 parts by mass or less, or 23.0 parts by mass or less with respect to 100 parts by mass of the ethylenically unsaturated monomer, from the viewpoint of further improving the ejection stability. It may be 15.0 parts by mass or less.

(Non-light-emitting ink composition)
The non-light emitting ink composition contains light scattering particles. On the other hand, the non-light-emitting ink composition does not contain light-emitting nanocrystal particles. Therefore, when light is incident on a pixel portion formed of the non-light-emitting ink composition (a pixel portion including a cured product of the non-light-emitting ink composition), light emitted from the pixel portion is substantially the same as the incident light. Having a wavelength of Therefore, the non-light-emitting ink composition is suitably used for forming a pixel portion having the same color as the light from the light source. For example, when the light from the light source is light having a wavelength in the range of 420 to 480 nm (blue light), the pixel portion formed by the non-light-emitting ink composition may be a blue pixel portion.

  Since the non-light-emitting ink composition of the present embodiment contains light-scattering particles, according to the pixel portion formed by the non-light-emitting ink composition, light incident on the pixel portion can be scattered, This makes it possible to reduce the difference in light intensity at the viewing angle of the light emitted from the pixel portion.

  In the non-light-emitting ink composition, light-scattering particles similar to the light-scattering particles used in the above-described light-emitting ink composition can be used. The light-scattering particles are selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, barium titanate and silica from the viewpoint that the light intensity difference at the viewing angle can be further reduced. It is preferable to include at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide and barium titanate, and it is more preferable to include titanium oxide. That is, the non-light emitting ink composition preferably contains titanium oxide particles as light scattering particles.

  As the light-scattering particles, the use of particles having a small directionality (for example, particles having a spherical shape, a tetrahedral shape, or the like) as the particle shape can further enhance the uniformity, fluidity, and light scattering properties of the ink composition. And it is preferable in that excellent ejection stability can be obtained.

  The average particle diameter (volume average diameter) of the light-scattering particles in the non-light-emitting ink composition is preferably from the viewpoint that sufficient light-scattering properties can be obtained and the light intensity difference at a viewing angle can be further reduced. Is 80 nm or more, more preferably 90 nm or more, and still more preferably 100 nm or more. The average particle size of the light scattering particles may be 150 nm or more, or may be 200 nm or more. The average particle diameter (volume average diameter) of the light-scattering particles in the luminescent ink composition is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm, from the viewpoint of excellent ejection stability. It is as follows. From these viewpoints, the average particle diameter (volume average diameter) of the light-scattering particles in the luminescent ink composition is 80 to 500 nm, 80 to 400 nm, 90 to 400 nm, 90 to 300 nm, or 100 to 300 nm. Good. From the viewpoint of easily obtaining such an average particle diameter (volume average diameter), the average particle diameter (volume average diameter) of the light-scattering particles used may be 80 nm or more, or may be 500 nm or less.

  The refractive index of the light-scattering particles is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0, from the viewpoint that the light intensity difference at the viewing angle can be further reduced. That is all. The refractive index of the light scattering particles may be 2.9 or less. The refractive index of the light-scattering particles is determined by the minimum declination method (precision spectrometer (GM type, GMR type) manufactured by Shimadzu Corporation) and the critical angle method (Abbe refractometer (KPR-30A type) manufactured by Shimadzu Corporation) And V-block method (a precision refractometer (KPR-3000, KPR-300, KPR-30V) manufactured by Shimadzu Corporation) or the like.

  The content of the light-scattering particles in the non-light-emitting ink composition is 1% by mass based on the weight of the non-volatile content of the non-light-emitting ink composition, from the viewpoint that the light intensity difference at a viewing angle can be further reduced. Or more, 5% by mass or more, or 10% by mass or more. The content of the light scattering particles is 80% by mass or less based on the mass of the non-volatile ink composition in terms of the non-emission ink composition, from the viewpoint of excellent ejection stability and the ability to further reduce light reflection. It may be 75% by mass or less, or 70% by mass or less.

  The non-light-emitting ink composition is a component other than the light-emitting nanocrystal particles (for example, a photopolymerizable compound, a thermosetting resin, a photopolymerization initiator, a curing agent, Curing accelerator, polymer dispersant, solvent, etc.). As these components, those similar to those used in the above-described luminescent ink composition can be used. The content of these components may be in the range described above for the luminescent ink composition.

  The non-light-emitting ink composition has a wavelength difference between light incident on a pixel portion (a cured product of the non-light-emitting ink composition) formed by the non-light-emitting ink composition and transmitted light from the pixel portion. (Color change). Therefore, the non-light-emitting ink composition preferably does not contain a coloring material such as a pigment, and in particular, a coloring material that exhibits a color different from the light absorbed by the luminescent nanocrystal particles used in the luminescent ink composition ( Pigment).

  The non-light-emitting ink composition has, for example, a light scattering property (a value obtained by dividing the scattered light transmittance by the linear light transmittance) of 10 or more with respect to light having a wavelength in the range of 420 to 480 nm after curing. . The light scattering property is preferably 20 or more, and more preferably 40 or more. The linear light transmittance and the scattered light transmittance used for calculating the light scattering property can be measured by the methods described in Examples.

  The viscosity at the ink temperature (for example, 23 ° C. or 40 ° C.) of the ink composition (light-emitting ink composition and non-light-emitting ink composition) included in the ink composition set described above during ink-jet printing is, for example, ink-jet printing. From the viewpoint of discharge stability at the time, the pressure may be 2 mPa · s or more, 5 mPa · s or more, or 7 mPa · s or more. The viscosity of the ink composition at the ink temperature during ink-jet printing may be 20 mPa · s or less, 15 mPa · s or less, or 12 mPa · s or less. The viscosity at the ink temperature at the time of inkjet printing of the ink composition is, for example, 2 to 20 mPa · s, 2 to 15 mPa · s, 2 to 12 mPa · s, 5 to 20 mPa · s, 5 to 15 mPa · s, 5 to 12 mPa · s. s, 7 to 20 mPa · s, 7 to 15 mPa · s, or 7 to 12 mPa · s. In the present specification, the viscosity of the ink composition is, for example, a viscosity measured by an E-type viscometer.

  When the viscosity of the ink composition at the time of ink-jet printing at the time of ink-jet printing is 2 mPa · s or more, since the meniscus shape of the ink-jet ink at the tip of the ink discharge hole of the discharge head is stable, the discharge control of the ink-jet ink (for example, Control of the amount and the timing of the discharge). On the other hand, when the viscosity of the ink composition at the time of ink-jet printing at the time of ink-jet printing is 20 mPa · s or less, the ink-jet ink can be smoothly discharged from the ink discharge holes.

  The surface tension of the ink composition is preferably a surface tension suitable for an ink jet system, specifically, preferably in the range of 20 to 40 mN / m, more preferably 25 to 35 mN / m. . By controlling the surface tension within the above range, the ejection control (for example, the control of the ejection amount and the ejection timing) becomes easy, and the occurrence of the flight bend can be suppressed. Note that the flight bend means that when the ink composition is ejected from the ink ejection holes, the landing position of the ink composition is shifted by 30 μm or more from the target position. When the surface tension is 40 mN / m or less, the meniscus shape at the tip of the ink ejection hole is stabilized, so that ejection control of the ink composition (for example, control of ejection amount and ejection timing) becomes easy. On the other hand, when the surface tension is 20 mN / m or more, the periphery of the ink ejection holes can be prevented from being contaminated with the inkjet ink, so that the occurrence of flight bending can be suppressed. That is, a pixel portion that is not accurately landed in the pixel portion formation region to be landed and is insufficiently filled with the ink composition occurs, or a pixel portion formation region (or a pixel portion) adjacent to the pixel portion formation region to be landed The ink composition does not land on the surface and color reproducibility is not reduced.

  When the ink composition (especially the luminescent ink composition) of the present embodiment is used as an ink composition for an ink jet system, the present invention is applied to a piezo jet type ink jet recording apparatus using a mechanical ejection mechanism using a piezoelectric element. Is preferred. In the piezo jet method, the ink composition is not instantaneously exposed to a high temperature during ejection. For this reason, the luminescent nanocrystal particles are unlikely to deteriorate, and the luminescent characteristics as expected are more easily obtained in the pixel portion (light conversion layer).

  In the above, one embodiment of the ink composition set for a color filter has been described. However, the ink composition set of the above-described embodiment can be used, for example, by a photolithography method in addition to the ink jet method. In this case, each ink composition in the ink composition set contains an alkali-soluble resin as a binder polymer.

  When the ink composition set is used by a photography method, first, the ink composition is applied on a substrate, and when the ink composition contains a solvent, the ink composition is further dried to form a coating film. . The coating film thus obtained is soluble in an alkali developing solution and is patterned by being treated with the alkali developing solution. At this time, since the alkali developer is mostly an aqueous solution from the viewpoint of, for example, ease of processing the waste liquid of the developer, the coating film of the ink composition is treated with the aqueous solution. On the other hand, in the case of an ink composition using luminescent nanocrystal particles (such as quantum dots), the luminescent nanocrystal particles are unstable with respect to water, and the luminescence (eg, fluorescence) is impaired by moisture. For this reason, in the present embodiment, an ink jet system which does not require treatment with an alkali developing solution (aqueous solution) is preferable.

  In addition, even when the coating film of the ink composition is not subjected to the treatment with the alkali developing solution, when the ink composition is alkali-soluble, the coating film of the ink composition easily absorbs moisture in the atmosphere. Therefore, when the luminescent ink composition is alkali-soluble, the luminescence (eg, fluorescence) of the luminescent nanocrystal particles (such as quantum dots) is deteriorated as time passes. From this viewpoint, in the present embodiment, the coating film of the ink composition (particularly, the luminescent ink composition) is preferably alkali-insoluble. That is, the ink composition of the present embodiment is preferably an ink composition capable of forming an alkali-insoluble coating film. Such an ink composition can be obtained by using an alkali-insoluble photopolymerizable compound and / or an alkali-insoluble thermosetting resin as the photopolymerizable compound and / or the thermosetting resin. When the coating film of the ink composition is alkali-insoluble, the amount of the coating film of the ink composition dissolved at 25 ° C. in a 1% by mass aqueous solution of potassium hydroxide is based on the total weight of the coating film of the ink composition. It means 30% by mass or less. The dissolution amount of the coating film of the ink composition is preferably 10% by mass or less, more preferably 3% by mass or less. Note that the ink composition is an ink composition capable of forming an alkali-insoluble coating film, which is obtained by applying the ink composition on a base material, and then drying at 80 ° C. for 3 minutes when a solvent is contained. It can be confirmed by measuring the above-mentioned dissolved amount of the obtained coating film having a thickness of 1 μm.

<Production method of ink composition set>
Next, a method for manufacturing the ink composition set of the above-described embodiment will be described. The method for producing an ink composition set includes a step of preparing a luminescent ink composition and a step of preparing a non-luminescent ink composition. The luminescent ink composition is obtained, for example, by mixing the components of the luminescent ink composition described above and performing a dispersion treatment. The non-light-emitting ink composition can be obtained by the same method as the light-emitting ink composition except that the light-emitting nanocrystal particles are not used. Hereinafter, as an example, a method for producing a luminescent ink composition containing light scattering particles and a polymer dispersant will be described.

  The method for producing a luminescent ink composition includes, for example, a first step of preparing a dispersion of light-scattering particles containing light-scattering particles and a polymer dispersant, and a dispersion of light-scattering particles and light emission. A second step of mixing the conductive nanocrystal particles. In this method, the dispersion of the light-scattering particles may further contain a photopolymerizable compound and / or a thermosetting resin, and in the second step, the photopolymerizable compound and / or the thermosetting resin is further mixed. May be. According to this method, the light scattering particles can be sufficiently dispersed. Therefore, the optical characteristics of the pixel portion can be improved, and a luminescent ink composition having excellent ejection stability can be easily obtained.

  In the step of preparing a dispersion of light-scattering particles, the light-scattering particles, a polymer dispersant, and, in some cases, a photopolymerizable compound and / or a thermosetting resin are mixed and dispersed. A dispersion of light scattering particles may be prepared. The mixing and dispersing treatment may be performed using a dispersing device such as a bead mill, a paint conditioner, a planetary stirrer, and a jet mill. It is preferable to use a bead mill or a paint conditioner from the viewpoint that the dispersibility of the light-scattering particles becomes good and the average particle diameter of the light-scattering particles can be easily adjusted to a desired range. By mixing the light-scattering particles and the polymer dispersant before mixing the light-emitting nanocrystal particles and the light-scattering particles, the light-scattering particles can be more sufficiently dispersed. Therefore, excellent ejection stability and excellent external quantum efficiency can be more easily obtained.

  The method for producing a luminescent ink composition includes, before the second step, a dispersion of luminescent nanocrystalline particles containing luminescent nanocrystalline particles and a photopolymerizable compound and / or a thermosetting resin. The method may further include a preparing step. In this case, in the second step, a dispersion of light-scattering particles and a dispersion of luminescent nanocrystal particles are mixed. In the step of preparing the dispersion of the luminescent nanocrystalline particles, the luminescent nanocrystalline particles are mixed with the photopolymerizable compound and / or the thermosetting resin, and the dispersion process is performed to perform the dispersion treatment. May be prepared. As the luminescent nanocrystal particles, luminescent nanocrystal particles having an organic ligand on the surface thereof may be used. That is, the luminescent nanocrystal particle dispersion may further include an organic ligand. The mixing and dispersing treatment may be performed using a dispersing device such as a bead mill, a paint conditioner, a planetary stirrer, and a jet mill. It is preferable to use a bead mill, a paint conditioner, or a jet mill from the viewpoint that the dispersibility of the luminescent nanocrystal particles becomes good and the average particle size of the luminescent nanocrystal particles can be easily adjusted to a desired range. According to this method, the luminescent nanocrystal particles can be sufficiently dispersed. For this reason, it is possible to improve the optical characteristics of the pixel portion and easily obtain an ink composition having excellent ejection stability.

  In this production method, components other than the above-described components (for example, a photosensitizing compound, a solvent, a phosphite triester compound, a thiol compound, and the like) may be further used. In this case, the other components may be contained in the luminescent nanocrystal particle dispersion, or may be contained in the light scattering particle dispersion. Further, other components may be mixed with the composition obtained by mixing the luminescent nanocrystal particle dispersion and the light scattering particle dispersion.

<Light conversion layer and color filter>
The light conversion layer of the present embodiment includes at least one type of luminescent pixel portion containing luminescent nanocrystal particles, and a non-luminescent pixel portion containing light scattering particles. The light conversion layer contains, as at least one kind of light-emitting pixel portion, light-emitting nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a light emission peak wavelength in the range of 605 to 665 nm. A second light-emitting pixel portion containing light-emitting nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a light emission peak wavelength in the range of 500 to 560 nm; , May be provided.

  Each of the luminescent pixel portion and the non-luminescent pixel portion in the light conversion layer of the present embodiment may include the light-scattering particles contained in the luminescent ink composition and the non-luminescent ink composition described above, It may contain a polymer of a photopolymerizable compound and / or a cured product of a thermosetting resin contained in the above-mentioned luminescent ink composition and non-luminescent ink composition. Such a light conversion layer can be obtained using the ink composition set of the embodiment described above. Hereinafter, the details of the light conversion layer and the color filter obtained by using the ink composition set of the above-described embodiment will be described with reference to the drawings. In the following description, the same or corresponding elements will be denoted by the same reference characters, without redundant description.

  FIG. 1 is a schematic sectional view of a color filter according to one embodiment. As shown in FIG. 1, the color filter 100 includes a base material 40 and a light conversion layer 30 provided on the base material 40. The light conversion layer 30 includes a plurality of pixel units 10 and a light shielding unit 20.

  The light conversion layer 30 includes, as the pixel unit 10, a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c. The first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c are arranged in a lattice so as to be repeated in this order. The light shielding unit 20 is provided between adjacent pixel units, that is, between the first pixel unit 10a and the second pixel unit 10b, between the second pixel unit 10b and the third pixel unit 10c, and between the adjacent pixel units. Is provided between the pixel section 10c and the first pixel section 10a. In other words, these adjacent pixel units are separated from each other by the light shielding unit 20.

  The first pixel portion 10a and the second pixel portion 10b are luminescent pixel portions each including a cured product of the luminescent ink composition described above. The cured product contains luminescent nanocrystal particles, light scattering particles, and a curing component. The curing component is a component obtained by polymerization of the photopolymerizable compound and / or curing of the thermosetting resin (polymerization, cross-linking, etc.), and a polymer of the photopolymerizable compound and / or a cured product of the thermosetting resin. Including. That is, the first pixel portion 10a includes the first curing component 13a, and the first light-emitting nanocrystal particles 11a and the first light-scattering particles 12a dispersed in the first curing component 13a, respectively. Including. Similarly, the second pixel portion 10b includes a second curing component 13b, a second light-emitting nanocrystal particle 11b and a second light-scattering particle 12b dispersed in the second curing component 13b, respectively. including. In the first pixel portion 10a and the second pixel portion 10b, the first hardening component 13a and the second hardening component 13b may be the same or different, and may be different from the first light-scattering particles 12a. The second light scattering particles 12b may be the same or different.

  The first luminescent nanocrystal particles 11a are red luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel unit 10a may be referred to as a red pixel unit for converting blue light into red light. The second luminescent nanocrystal particles 11b are green luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 10b may be referred to as a green pixel portion for converting blue light into green light.

  The content of the luminescent nanocrystal particles in the luminescent pixel portion is based on the total mass of the cured product of the luminescent ink composition, from the viewpoint that the effect of improving external quantum efficiency is excellent and the viewpoint that excellent luminous intensity is obtained. It is preferably at least 5% by mass. From a similar viewpoint, the content of the luminescent nanocrystal particles may be 10% by mass or more, or 15% by mass or more, based on the total mass of the cured product of the luminescent ink composition. It may be 20% by mass or more. The content of the luminescent nanocrystal particles is preferably 80% by mass or less, based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of excellent reliability of the pixel portion and excellent luminescence intensity. It is. From the same viewpoint, the content of the luminescent nanocrystal particles may be 75% by mass or less, or 70% by mass or less, based on the total mass of the cured product of the luminescent ink composition. It may be 60% by mass or less.

  The content of the light-scattering particles in the light-emitting pixel portion may be 0.1% by mass or more based on the total mass of the cured product of the light-emitting ink composition, from the viewpoint of improving the external quantum efficiency. 1% by mass or more, 3% by mass or more, or 5% by mass or more. The content of the light-scattering particles is 60% by mass or less based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of improving the external quantum efficiency and improving the reliability of the pixel portion. May be 50% by mass or less, 40% by mass or less, or 30% by mass or less.

  The third pixel portion 10c is a non-light-emitting pixel portion including a cured product of the above-described non-light-emitting ink composition. The cured product contains light scattering particles and a curing component. The curing component is a component obtained by polymerization of the photopolymerizable compound and / or curing of the thermosetting resin (polymerization, cross-linking, etc.), and a polymer of the photopolymerizable compound and / or a cured product of the thermosetting resin. Including. That is, the third pixel portion 10c includes the third hardening component 13c and the third light scattering particles 12c dispersed in the third hardening component 13c. The third light-scattering particles 12c may be the same as or different from the first light-scattering particles 12a and the second light-scattering particles 12b.

  The third pixel portion 10c has, for example, a transmittance of 30% or more for light having a wavelength in the range of 420 to 480 nm. Therefore, the third pixel portion 10c functions as a blue pixel portion when using a light source that emits light having a wavelength in the range of 420 to 480 nm. Note that the transmittance of the third pixel portion 10c can be measured with a microspectroscope.

  The content of the light-scattering particles in the non-light-emitting pixel portion is 1% by mass based on the total mass of the cured product of the non-light-emitting ink composition, from the viewpoint that the light intensity difference at the viewing angle can be further reduced. Or more, 5% by mass or more, or 10% by mass or more. The content of the light-scattering particles may be 80% by mass or less, and 75% by mass or less based on the total mass of the cured product of the non-light-emitting ink composition, from the viewpoint of further reducing light reflection. Or 70% by mass or less.

  The thickness of the pixel portion (the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c) is, for example, 1 μm or more, 2 μm or more, or 3 μm or more. May be. The thickness of the pixel portion (the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c) may be, for example, 30 μm or less, 20 μm or less, or 15 μm or less. May be.

  The light-shielding portion 20 is a so-called black matrix provided for the purpose of separating adjacent pixel portions to prevent color mixture and preventing light from leaking from a light source. The material constituting the light-shielding portion 20 is not particularly limited. In addition to a metal such as chromium, curing of a resin composition containing a binder polymer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments. Objects can be used. As the binder polymer used here, one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, photosensitive resin, O / W Emulsion-type resin compositions (for example, those obtained by emulsifying reactive silicone) can be used. The thickness of the light-shielding portion 20 may be, for example, 0.5 μm or more and 10 μm or less.

  The base material 40 is a transparent base material having optical transparency, for example, a transparent glass substrate such as quartz glass, Pyrex (registered trademark) glass, a synthetic quartz plate, a transparent resin film, a resin film for optical use, or the like. A flexible substrate or the like can be used. Among these, it is preferable to use a glass substrate made of non-alkali glass containing no alkali component in the glass. Specifically, “7059 glass”, “1737 glass”, “Eagle 200” and “Eagle XG” manufactured by Corning, “AN100” manufactured by Asahi Glass, “OA-10G” and “OA-10G” manufactured by NEC Corporation OA-11 "is preferred. These are materials having a small coefficient of thermal expansion and are excellent in dimensional stability and workability in high-temperature heat treatment.

  The color filter 100 including the light conversion layer 30 described above is suitably used when a light source that emits light having a wavelength in the range of 420 to 480 nm is used.

  The color filter 100 forms, for example, the light-shielding portions 20 in a pattern on the base material 40, and then applies the ink composition of the above-described embodiment to the pixel portion formation region defined by the light-shielding portions 20 on the base material 40. (Ink jet ink) is selectively adhered by an ink jet method, and the ink composition is cured by irradiation with active energy rays or heating.

  The method of forming the light-shielding portion 20 is to form a metal thin film such as chromium or a thin film of a resin composition containing light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one surface side of the base material 40. Then, a method of patterning the thin film and the like can be mentioned. The metal thin film can be formed by, for example, a sputtering method, a vacuum evaporation method, or the like, and the thin film of the resin composition containing light-shielding particles can be formed by, for example, a method such as coating or printing. As a method of performing patterning, a photolithography method or the like can be given.

  Examples of the ink jet method include a bubble jet (registered trademark) method using an electrothermal converter as an energy generating element, a piezo jet method using a piezoelectric element, and the like.

When the ink composition is cured by irradiation with active energy rays (for example, ultraviolet rays), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED, or the like may be used. The wavelength of the irradiation light may be, for example, 200 nm or more, and may be 440 nm or less. The exposure amount may be, for example, 10 mJ / cm ² or more and 4000 mJ / cm ² or less.

  The drying temperature for volatilizing the solvent may be, for example, 50 ° C. or higher and 150 ° C. or lower. The drying time may be, for example, not less than 3 minutes and not more than 30 minutes.

  When the ink composition is cured by heating, the heating temperature may be, for example, 110 ° C. or higher and 250 ° C. or lower. The heating time may be, for example, not less than 10 minutes and not more than 120 minutes.

  As described above, one embodiment of the color filter, the light conversion layer, and the method of manufacturing the same has been described, but the present invention is not limited to the above embodiment.

  For example, the light conversion layer may include, in addition to the third pixel portion 10c, a pixel portion (blue pixel portion) containing a cured product of an ink composition containing blue light-emitting nanocrystal particles. Further, the light conversion layer may include a pixel portion (for example, a yellow pixel portion) including a cured product of a luminescent ink composition containing nanocrystalline particles that emit light of a color other than red, green, and blue. Good. In these cases, each of the luminescent nanocrystal particles contained in each luminescent pixel portion of the light conversion layer preferably has an absorption maximum wavelength in the same wavelength region.

  In addition, at least a part of the pixel portion of the light conversion layer may include a cured product of a composition containing a pigment other than the luminescent nanocrystal particles.

  Further, the color filter may include an ink-repellent layer made of a material having an ink-repellent property, which is narrower than the light-shielding portion, on the pattern of the light-shielding portion. Also, instead of providing an ink-repellent layer, a photocatalyst-containing layer as a wettability variable layer is formed in a solid coating shape in a region including a pixel portion formation region, and light is applied to the photocatalyst-containing layer via a photomask. Exposure may be performed by irradiation to selectively increase the ink affinity of the pixel portion formation region. Examples of the photocatalyst include titanium oxide and zinc oxide.

  Further, the color filter may include an ink receiving layer containing hydroxypropylcellulose, polyvinyl alcohol, gelatin or the like between the base material and the pixel portion.

  Further, the color filter may include a protective layer on the pixel portion. This protective layer flattens the color filter and prevents components contained in the pixel portion, or components contained in the pixel portion and components contained in the photocatalyst containing layer from being eluted into the liquid crystal layer. It is provided. As a material constituting the protective layer, a material used as a known protective layer for a color filter can be used.

  In the production of the color filter and the light conversion layer, the pixel portion may be formed by a photolithography method instead of the ink jet method. In this case, first, the ink composition (light-emitting ink composition or non-light-emitting ink composition) is applied to the substrate in a layer form to form an ink composition layer. Next, the ink composition layer is exposed to light in a pattern and then developed using a developer. In this manner, a pixel portion made of a cured product of the ink composition is formed. Since the developer is usually alkaline, an alkali-soluble material is used as a material for the ink composition. However, from the viewpoint of material use efficiency, the inkjet method is superior to the photolithography method. This is because, in the photolithography method, approximately 2/3 or more of the material is removed in principle, and the material is wasted. For this reason, in this embodiment, it is preferable that the pixel portion is formed by an inkjet method using an inkjet ink.

  In addition, the luminescent pixel portion of the light conversion layer of the present embodiment may further contain a pigment having substantially the same color as the luminescent color of the luminescent nanocrystal particles, in addition to the above-described luminescent nanocrystal particles. For example, when a pixel portion containing luminescent nanocrystal particles that absorb and emit blue light is employed as a pixel portion of a liquid crystal display element, as light from a light source, blue light or quasi-white light having a peak at 450 nm is used. However, when the concentration of the luminescent nanocrystal particles in the pixel portion is not sufficient, the light from the light source passes through the light conversion layer when the liquid crystal display element is driven. The transmitted light (blue light, leaked light) from the light source and the light emitted from the luminescent nanocrystal particles are mixed. From the viewpoint of preventing a decrease in color reproducibility due to the occurrence of such color mixture, a pigment may be contained in the pixel portion of the light conversion layer. In order to include the pigment in the pixel portion, the luminescent ink composition may include the pigment.

  Further, among the red pixel portion (R), the green pixel portion (G), and the blue pixel portion (B) in the light conversion layer of the present embodiment, one kind of luminescent pixel portion is formed by luminescent nanocrystal particles. A pixel portion containing a coloring material without containing it may be used. As the coloring material that can be used here, a known coloring material can be used. For example, as the coloring material used for the red pixel portion (R), a diketopyrrolopyrrole pigment and / or an anionic red organic dye are used. No. Examples of the coloring material used for the green pixel portion (G) include at least one selected from the group consisting of a copper halide phthalocyanine pigment, a phthalocyanine green dye, and a mixture of a phthalocyanine blue dye and an azo yellow organic dye. Examples of the coloring material used for the blue pixel portion (B) include an ε-type copper phthalocyanine pigment and / or a cationic blue organic dye. When used in the light conversion layer, the amount of these coloring materials used is 1 to 5 masses based on the total mass of the pixel portion (cured product of the ink composition) from the viewpoint of preventing a decrease in transmittance. %.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to only the following examples.

<Preparation of light scattering particle dispersion 1>
12 g of light scattering particles (titanium oxide, trade name: MT-700B, manufactured by Teika Co., Ltd., average particle diameter (volume average diameter): 80 nm, refractive index 2.72), and a polymer dispersant (trade name: DISPERBYK) (2-1664, manufactured by BYK-Chemie) and 1,4-butanediol diacetate to prepare a mixed solution having a nonvolatile content of 44% by mass. After adding zirconia beads (diameter: 1.25 mm) to the mixture, the mixture was shaken for 2 hours using a paint conditioner to perform a dispersion treatment of the mixture. The zirconia beads were removed with a polyester mesh filter to obtain a light scattering particle dispersion 1.

<Preparation of light scattering particle dispersion 2>
Light scattering particles were used except that titanium oxide (trade name: MPT-141, manufactured by Ishihara Sangyo Co., Ltd., average particle diameter (volume average diameter): 100 nm, refractive index 2.72) was used as the light scattering particles. A light-scattering particle dispersion 2 was obtained in the same manner as in the preparation of the dispersion 1.

<Preparation of light scattering particle dispersion 3>
Light scattering particle dispersion was used except that titanium oxide (trade name: JR-405, manufactured by Teica Corporation, average particle diameter (volume average diameter): 210 nm, refractive index 2.72) was used as the light scattering particles. Light scattering particle dispersion 3 was obtained in the same manner as in preparation of body 1.

<Preparation of light scattering particle dispersion 4>
Light scattering particle dispersion is used except that titanium oxide (trade name: JR-805, manufactured by Teica Corporation, average particle diameter (volume average diameter): 290 nm, refractive index 2.72) is used as the light scattering particles. Light scattering particle dispersion 4 was obtained in the same manner as in preparation of body 1.

<Preparation of thermosetting resin solution 1>
0.528 g of a thermosetting resin (trade name: EPICLON N-865, manufactured by DIC Corporation), 0.221 g of a curing agent (trade name: PHENOLITE TD-2131, manufactured by DIC Corporation), and a curing catalyst (trade name: 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.0006 g) was dissolved in 1,4-butanediol diacetate to obtain a thermosetting resin solution 1 (nonvolatile content: 30% by mass). Got.

<Preparation of thermosetting resin solution 2>
0.628 g of a thermosetting resin (trade name: Finedick A-254, manufactured by DIC Corporation) and a curing agent (trade name: 4-methylcyclohexane-1,2-dicarboxylic anhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) ) 0.105 g and 0.008 g of a curing catalyst (trade name: N, N-dimethylbenzylamine, manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 1,4-butanediol diacetate to obtain a thermosetting resin. Solution 2 (nonvolatile content concentration: 30% by mass) was obtained.

<Example 1>
After uniformly mixing 1.37 g of the light-scattering particle dispersion 1 (non-volatile concentration: 44% by mass) and 2.66 g of the thermosetting resin solution 1 (non-volatile concentration: 30% by mass), the mixture was mixed. The ink composition (inkjet ink) of Example 1 was obtained by filtering with a filter having a pore size of 5 μm. The content of the light-scattering particles was 40% by mass based on the mass of the nonvolatile components of the ink composition.

<Examples 2 to 4>
The ink compositions (inkjet inks) of Examples 2 to 4 were obtained in the same manner as in Example 1 except that the light scattering particle dispersions 2 to 4 were used instead of the light scattering particle dispersion 1. Was. The content of the light-scattering particles was 40% by mass based on the mass of the nonvolatile components of the ink composition.

<Example 5>
An ink composition (inkjet ink) of Example 5 was obtained in the same manner as in Example 1, except that the thermosetting resin solution 2 was used instead of the thermosetting resin solution 1. The content of the light-scattering particles was 40% by mass based on the mass of the nonvolatile components of the ink composition.

<Example 6>
Except that the compounding amount of the light scattering particle dispersion 2 was changed to 2.36 g and the compounding amount of the thermosetting resin solution 2 was changed to 1.21 g, the ink composition of Example 6 was changed in the same manner as in Example 5. (Ink-jet ink) was obtained. The content of the light-scattering particles was 70% by mass based on the mass of the nonvolatile components of the ink composition.

<Example 7>
Except that the compounding amount of the light scattering particle dispersion 2 was changed to 0.69 g and the compounding amount of the thermosetting resin solution 2 was changed to 3.66 g, the ink composition of Example 7 was changed in the same manner as in Example 5. (Ink-jet ink) was obtained. The content of the light-scattering particles was 20% by mass based on the mass of the nonvolatile components of the ink composition.

<Comparative Example 1>
An ink composition (inkjet ink) of Comparative Example 1 was obtained in the same manner as in Example 1, except that the light-scattering particle dispersion was not used.

<Evaluation 1>
(Preparation of evaluation sample)
The ink compositions of Examples 1 to 7 and Comparative Example 1 were applied to a glass substrate in the air by a spin coater so that the film thickness after drying was 5 μm. The coating film was heated and cured at 180 ° C. to form a layer (cured material layer) made of a cured product of the ink composition on a glass substrate. The substrate having the obtained cured product layer was used as an evaluation sample.

(Light scattering evaluation)
The linear light transmittance and the scattered light transmittance were measured according to the following procedure, and the value obtained by dividing the scattered light transmittance by the linear light transmittance was evaluated as light scattering. In the evaluation of the light scattering property, the case where the light scattering property (the value obtained by dividing the scattered light transmittance by the linear light transmittance) is 40 or more is ○, and the case where the light scattering property is 10 or more and less than 40 is △ or less. The case was marked as x.

[Linear light transmittance]
Examples 1 to 7 and Comparative Examples were carried out by detecting a transmitted light at a wavelength of 450 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a direct incidence detector as a detector. The cured product of the first ink composition was measured for linear light transmittance. Table 1 shows the results.

[Scattered light transmittance]
Examples 1 to 7 and Comparative Examples were performed by detecting transmitted light at a wavelength of 450 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a φ60 standard integrating sphere as a detector. The scattered light transmittance of the cured product of the first ink composition was measured. Table 1 shows the results.

Example 8
(Preparation of InP / ZnSeS / ZnS Nanocrystalline Particle Dispersion with Red Emission)
[Preparation of indium laurate solution]
10 g of 1-octadecene (ODE), 146 mg (0.5 mmol) of indium acetate and 300 mg (1.5 mmol) of lauric acid were added to the reaction flask to obtain a mixture. The mixture was heated at 140 ° C. for 2 hours under vacuum to obtain a clear solution (indium laurate solution). This solution was kept in a glove box at room temperature until needed. Since indium laurate has low solubility at room temperature and tends to precipitate, when the indium laurate solution is used, the precipitated indium laurate in the solution (ODE mixture) is heated to about 90 ° C. to obtain a transparent solution. After forming the solution, the desired amount was weighed and used.

[Preparation of core (InP core) of red light-emitting nanocrystal particles]
5 g of trioctylphosphine oxide (TOPO), 1.46 g (5 mmol) of indium acetate and 3.16 g (15.8 mmol) of lauric acid were added to the reaction flask to obtain a mixture. The mixture was heated at 160 ° C. for 40 minutes under a nitrogen (N ₂ ) environment, and then heated at 250 ° C. for 20 minutes under vacuum. Next, the reaction temperature (temperature of the mixture) was increased to 300 ° C. under a nitrogen (N ₂ ) environment. At this temperature, a mixture of 3 g of 1-octadecene (ODE) and 0.25 g (1 mmol) of tris (trimethylsilyl) phosphine was quickly introduced into the reaction flask, maintaining the reaction temperature at 260 ° C. After 5 minutes, the reaction was stopped by removing the heater, and the resulting reaction solution was cooled to room temperature. Next, 8 ml of toluene and 20 ml of ethanol were added to the reaction solution in the glove box. Subsequently, centrifugation was performed to precipitate InP nanocrystal particles, and then the supernatant was decanted to obtain InP nanocrystal particles. Next, the obtained InP nanocrystal particles were dispersed in hexane. Thus, a dispersion (hexane dispersion) containing 5% by mass of InP nanocrystal particles was obtained.

The hexane dispersion of InP nanocrystal particles obtained above and the indium laurate solution were charged into a reaction flask to obtain a mixture. The charged amounts of the hexane dispersion solution of the InP nanocrystal particles and the indium laurate solution were adjusted to be 0.5 g (25 mg of InP nanocrystal particles) and 5 g (178 mg of indium laurate), respectively. After allowing the mixture to stand at room temperature under vacuum for 10 minutes, the inside of the flask was returned to normal pressure with nitrogen gas, the temperature of the mixture was raised to 230 ° C, and the temperature was maintained for 2 hours to remove hexane from the inside of the flask. . Next, the temperature inside the flask was raised to 250 ° C., and a mixture of 3 g of 1-octadecene (ODE) and 0.03 g (0.125 mmol) of tris (trimethylsilyl) phosphine was rapidly introduced into the reaction flask, and the reaction temperature was increased to 230 ° C. Maintained. After 5 minutes, the reaction was stopped by removing the heater, and the resulting reaction solution was cooled to room temperature. Next, 8 ml of toluene and 20 ml of ethanol were added to the reaction solution in the glove box. Subsequently, centrifugal separation is performed to precipitate InP nanocrystal particles (InP core) serving as the core of the red light-emitting InP / ZnSeS / ZnS nanocrystal particles, and then the supernatant is decanted to obtain InP nanocrystal particles (InP core). Got. Next, the obtained InP nanocrystal particles (InP core) were dispersed in hexane to obtain a dispersion (hexane dispersion) containing 5% by mass of InP nanocrystal particles (InP core).

[Formation of Shell (ZnSeS / ZnS Shell) of Red Emitting Nanocrystal Particles]
After adding 2.5 g of the hexane dispersion liquid of InP nanocrystal particles (InP core) obtained above to the reaction flask, 0.7 g of oleic acid was added to the reaction flask at room temperature, and the temperature was raised to 80 ° C. For 2 hours. Next, 14 mg of diethylzinc, 8 mg of bis (trimethylsilyl) selenide and 7 mg of hexamethyldisilatiane (ZnSeS precursor solution) dissolved in 1 ml of ODE are dropped into the reaction mixture, and the temperature is raised to 200 ° C. and maintained for 10 minutes. As a result, a ZnSeS shell having a thickness of 0.5 monolayer was formed.

  Then the temperature was raised to 140 ° C. and held for 30 minutes. Next, in this reaction mixture, a ZnS precursor solution obtained by dissolving 69 mg of diethyl zinc and 66 mg of hexamethyldisilatiane in 2 ml of ODE was dropped, and the temperature was raised to 200 ° C. and maintained for 30 minutes. A two monolayer ZnS shell was formed. Ten minutes after the dropwise addition of the ZnS precursor solution, the reaction was stopped by removing the heater. Next, the reaction mixture was cooled to room temperature, and the resulting white precipitate was removed by centrifugation, whereby a transparent nanocrystal particle dispersion liquid (InP / ZnSeS) in which red light-emitting InP / ZnSeS / ZnS nanocrystal particles were dispersed. / ODE dispersion of ZnS nanocrystal particles).

[Synthesis of Organic Ligands for InP / ZnSeS / ZnS Nanocrystal Particles]
(Synthesis of organic ligand)
After charging JEFAMINE M-1000 (manufactured by Huntsman) into the flask, succinic anhydride (manufactured by Sigma-Aldrich) in an equimolar amount to JEFAMINE M-1000 was added thereto while stirring in a nitrogen gas environment. The internal temperature of the flask was raised to 80 ° C., and the mixture was stirred for 8 hours to obtain an organic ligand represented by the following formula (A) as a pale yellow viscous oil.

[Preparation of InP / ZnSeS / ZnS Nanocrystalline Particle Dispersion with Red Emission by Ligand Exchange]
30 mg of the organic ligand was added to 1 ml of the ODE dispersion of the InP / ZnSeS / ZnS nanocrystal particles obtained above. Next, ligand exchange was performed by heating at 90 ° C. for 5 hours. With the progress of ligand exchange, aggregation of nanocrystal particles was observed. After the ligand exchange, the supernatant was decanted to obtain nanocrystal particles. Next, 3 ml of ethanol was added to the obtained nanocrystal particles, and the mixture was ultrasonically dispersed to be redispersed. 10 ml of n-hexane was added to 3 ml of the ethanol dispersion liquid of the obtained nanocrystal particles. Then, after nanocrystal particles were precipitated by centrifugation, the supernatant was decanted and dried under vacuum to obtain nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the organic ligand). The content of the organic ligand in the total amount of the nanocrystal particles modified with the organic ligand was about 30% by mass. The obtained nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the organic ligand) are dispersed in 1,4-butanediol diacetate so that the content in the dispersion becomes 30% by mass. Thereby, a red light-emitting nanocrystal particle dispersion was obtained.

(Preparation of InP / ZnSeS / ZnS Nanocrystalline Particle Dispersion with Green Emission)
[Synthesis of Green Emitting Nanocrystalline Particle Core (InP Core)]
5 g of trioctylphosphine oxide (TOPO), 1.46 g (5 mmol) of indium acetate and 3.16 g (15.8 mmol) of lauric acid were added to the reaction flask to obtain a mixture. The mixture was heated at 160 ° C. for 40 minutes under a nitrogen (N ₂ ) environment, and then heated at 250 ° C. for 20 minutes under vacuum. Next, the reaction temperature (temperature of the mixture) was increased to 300 ° C. under a nitrogen (N ₂ ) environment. At this temperature, a mixture of 3 g of 1-octadecene (ODE) and 0.25 g (1 mmol) of tris (trimethylsilyl) phosphine was quickly introduced into the reaction flask, maintaining the reaction temperature at 260 ° C. After 5 minutes, the reaction was stopped by removing the heater, and the resulting reaction solution was cooled to room temperature. Next, 8 ml of toluene and 20 ml of ethanol were added to the reaction solution in the glove box. Subsequently, centrifugation was performed to precipitate InP nanocrystal particles (InP core), and then the supernatant was decanted to obtain InP nanocrystal particles (InP core). Next, the obtained InP nanocrystal particles (InP core) were dispersed in hexane to obtain a dispersion (hexane dispersion) containing 5% by mass of InP nanocrystal particles (InP core).

[Synthesis of Green Light Emitting Nanocrystal Particle Shell (ZnSeS / ZnS Shell)]
After adding 2.5 g of the hexane dispersion liquid of InP nanocrystal particles (InP core) obtained above to the reaction flask, 0.7 g of oleic acid was added to the reaction flask at room temperature, and the temperature was raised to 80 ° C. Was. Then, 14 mg of diethyl zinc, 8 mg of bis (trimethylsilyl) selenide and 7 mg of hexamethyldisilatiane (ZnSeS precursor solution) dissolved in 1 ml of ODE were dropped into the reaction mixture to give a 0.5 monolayer thickness. A ZnSeS shell was formed.

  After the dropwise addition of the ZnSeS precursor solution, the reaction temperature was maintained at 80 ° C. for 10 minutes. Then the temperature was raised to 140 ° C. and held for 30 minutes. Next, in this reaction mixture, a ZnS precursor solution obtained by dissolving 69 mg of diethyl zinc and 66 mg of hexamethyldisilatiane in 2 ml of ODE was added dropwise to form a ZnS shell having a thickness of 2 monolayers. . Ten minutes after the dropwise addition of the ZnS precursor solution, the reaction was stopped by removing the heater. Next, the reaction mixture was cooled to room temperature, and the resulting white precipitate was removed by centrifugation, whereby a transparent nanocrystal particle dispersion (ODE dispersion liquid) in which green luminescent InP / ZnSeS / ZnS nanocrystal particles were dispersed was obtained. ) Got.

[Preparation of green light-emitting InP / ZnSeS / ZnS nanocrystal particle dispersion by ligand exchange]
30 mg of the organic ligand was added to 1 ml of the ODE dispersion of nanocrystal particles obtained above. Next, ligand exchange was performed by heating at 90 ° C. for 5 hours. With the progress of ligand exchange, aggregation of nanocrystal particles was observed. After the ligand exchange was completed, the supernatant was decanted, and 3 ml of ethanol was added to the nanocrystal particles, followed by ultrasonic treatment to redisperse. 10 ml of n-hexane was added to 3 ml of the ethanol dispersion liquid of the obtained nanocrystal particles. Then, after nanocrystal particles were precipitated by centrifugation, the supernatant was decanted and dried under vacuum to obtain nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the organic ligand). The content of the organic ligand in the total amount of the nanocrystal particles modified with the organic ligand was 35% by mass. The obtained nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the organic ligand) are dispersed in 1,4-butanediol diacetate so that the content in the dispersion becomes 30% by mass. Thus, a green light-emitting nanocrystal particle dispersion was obtained.

(Preparation of Red Emissive Ink Composition (Inkjet Ink))
4.50 g of the red luminescent nanocrystal particle dispersion, 1.50 g of the light scattering particle dispersion 1, and 2.50 g of the thermosetting resin solution 1 were uniformly mixed in a vessel filled with argon gas. After mixing, the mixture was filtered with a filter having a pore size of 5 μm in a glove box. Further, argon gas was introduced into a container containing the obtained filtrate, and the inside of the container was saturated with argon gas. Next, the pressure was reduced to remove the argon gas, thereby obtaining an ink composition (red light-emitting ink composition).

(Preparation of Green Emissive Ink Composition (Inkjet Ink))
4.13 g of the green light-emitting nanocrystal particle dispersion, 1.38 g of the light scattering particle dispersion 1, and 2.29 g of the thermosetting resin solution 1 were uniformly mixed in a vessel filled with argon gas. After mixing, the mixture was filtered with a filter having a pore size of 5 μm in a glove box. Further, argon gas was introduced into a container containing the obtained filtrate, and the inside of the container was saturated with argon gas. Then, the pressure was reduced to remove the argon gas, thereby obtaining an ink composition (green light-emitting ink composition).

(Production of light conversion filter with pattern)
The ink composition obtained in Example 1, and the red light emitting ink composition and the green light emitting ink composition prepared above were prepared as an ink composition set of Example 8.

Next, a substrate (BM substrate) having a light-shielding portion called a black matrix (BM) was manufactured by the following procedure. That is, after a black resist ("CFPR BK" manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on a glass substrate ("OA-10G" manufactured by Nippon Electric Glass) made of non-alkali glass, pattern exposure, development and baking are performed. As a result, a patterned light-shielding portion was formed. The exposure was performed by irradiating the black resist with ultraviolet rays at an exposure amount of 200 mJ / cm ² . The pattern of the light-shielding portion was a pattern having openings corresponding to sub-pixels of 200 μm × 600 μm, the line width was 20 μm, and the thickness was 2.6 μm.

  Next, after printing the ink composition obtained in Example 1, and the red light-emitting ink composition and the green light-emitting ink composition prepared above in the openings on the BM substrate by an ink jet method, The ink solvent was volatilized by heating at 100 ° C. for 10 minutes. Then, it was heated at 180 ° C. for 10 minutes in a nitrogen atmosphere. Thereby, the ink composition was cured, and the pixel portion composed of the cured product of the ink composition of Example 1, the pixel portion composed of the pixel portion of the red luminescent ink composition, and the cured product of the green luminescent ink composition were obtained. Pixel portion was formed. The thickness of each pixel portion was 2.1 μm. Through the above operation, a light conversion filter with a pattern (light conversion layer) was obtained.

<Examples 9 to 14 and Comparative Example 2>
The patterns of Examples 9 to 14 and Comparative Example 2 were the same as in Example 8 except that the ink compositions of Examples 2 to 7 and Comparative Example 1 were used instead of the ink compositions of Example 1. A light conversion filter was obtained.

<Evaluation 2>
Using a blue LED (peak emission wavelength: 450 nm) manufactured by CCS Co., Ltd. as a surface emission light source, a blue light was applied to the obtained patterned light conversion filter from the glass substrate side (the side opposite to the pixel portion side). Was irradiated. Light emitted from the pixel portion of the light conversion filter was visually observed from a direction of 0 ° and an oblique direction of about 80 ° with respect to the light from the light source, and the presence or absence of a color change at each viewing angle was evaluated. In Comparative Example 2, the color change is large between the 0 ° direction and the oblique direction of about 80 ° (there is color viewing angle dependency), whereas in Examples 8 to 14, the color change is small (the color viewing angle dependency). Sex).

DESCRIPTION OF SYMBOLS 10 ... Pixel part, 10a ... First pixel part, 10b ... Second pixel part, 10c ... Third pixel part, 11a ... First luminescent nanocrystal particle, 11b ... Second luminescent nanocrystal particle , 12a: first light scattering particles, 12b: second light scattering particles, 12c: third light scattering particles, 20: light shielding part, 30: light conversion layer, 40: base material, 100: color filter.

Claims (15)

  An ink composition set comprising at least one luminescent ink composition containing luminescent nanocrystalline particles and a non-luminescent ink composition containing light scattering particles. As the at least one luminescent ink composition,
A first luminescent ink composition containing luminescent nanocrystalline particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm;
A second luminescent ink composition containing luminescent nanocrystalline particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm;
The ink composition set according to claim 1, comprising:   The ink composition set according to claim 1, wherein the light-scattering particles have an average particle size of 80 nm or more. 4.   The ink composition set according to any one of claims 1 to 3, wherein the light-scattering particles have a refractive index of 1.5 or more.   The ink composition set according to any one of claims 1 to 4, wherein the light scattering particles are titanium oxide particles.   The ink composition set according to any one of claims 1 to 5, wherein the luminescent ink composition and the non-luminescent ink composition further include a photopolymerizable compound and / or a thermosetting resin.   The ink composition set according to any one of claims 1 to 6, which is used for forming a light conversion layer.   The ink composition set according to any one of claims 1 to 7, which is used in an inkjet method.   A light conversion layer comprising: at least one kind of luminescent pixel portion containing luminescent nanocrystal particles; and a non-luminescent pixel portion containing light scattering particles. As the at least one kind of luminescent pixel portion,
A first luminescent pixel portion containing luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm;
A second luminescent pixel portion containing luminescent nanocrystalline particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm;
The light conversion layer according to claim 9, comprising:   The light conversion layer according to claim 9, wherein the light-scattering particles have an average particle diameter of 80 nm or more.   The light conversion layer according to any one of claims 9 to 11, wherein the light-scattering particles have a refractive index of 1.5 or more.   The light conversion layer according to any one of claims 9 to 12, wherein the light scattering particles are titanium oxide particles.   The light-emitting pixel portion and the non-light-emitting pixel portion further include a curing component including a polymer of a photopolymerizable compound and / or a cured product of a thermosetting resin. 3. The light conversion layer according to 1. A color filter comprising the light conversion layer according to claim 9.

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