TW201835254A - Ink composition, light conversion layer, and color filter - Google Patents

Abstract

An ink composition containing luminescent nanocrystal particles, light-scattering particles, and a photopolymerizable compound and/or thermosetting resin.

Description

   Ink composition, light conversion layer and color filter   

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

Conventionally, a color filter pixel portion in a display such as a liquid crystal display device uses a hardening resist material containing, for example, red organic pigment particles or green organic pigment particles and an alkali-soluble resin and / or an acrylic monomer. Photolithography.

In recent years, there has been a strong demand for low power consumption of displays. The industry is actively researching the use of luminescent nanocrystalline particles such as quantum dots, quantum rods, and other inorganic phosphor particles instead of the red organic pigment particles or green organic pigment particles. A method for forming a pixel portion of a color filter such as a red pixel and a green pixel.

In addition, in the manufacturing method of the color filter by the photolithography method described above, the manufacturing method is characterized in that there is a change in resist material other than the pixel portion containing relatively expensive luminescent nanocrystalline particles. The disadvantage of having to waste. Under these circumstances, in order to eliminate the waste of the resist material as described above, research into forming a pixel portion of a light conversion substrate by an inkjet method has been started (Patent Document 1).

[Prior technical literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2008/001693

When a color filter pixel portion (hereinafter also simply referred to as a "pixel portion") is formed by using an ink composition of luminescent nanocrystalline particles, light from a light source may not be absorbed by the luminescent nanocrystalline particles. If it leaks from the pixel part. Since such light leakage reduces the color reproducibility of the pixel portion, it must be minimized.

Therefore, an object of the present invention is to provide an ink composition capable of reducing light leakage, and a light conversion layer and a color filter using the ink composition.

One aspect of the present invention relates to an ink composition containing light-emitting nanocrystalline particles, light-scattering particles, a photopolymerizable compound, and / or a thermosetting resin. With this ink composition, light leakage in the pixel portion can be reduced.

The ink composition may further contain a polymer dispersant. The weight average molecular weight of the polymer dispersant may be 1,000 or more.

When the ink composition contains a photopolymerizable compound, the photopolymerizable compound may be a photoradical polymerizable compound or a photocationic polymerizable compound. The photopolymerizable compound may be alkali-insoluble.

When the ink composition contains a thermosetting resin, the thermosetting resin may be alkali-insoluble.

The ink composition may be an ink composition capable of forming an alkali-insoluble coating film.

The average particle diameter of the light-scattering particles may be 0.05 to 1.0 μm, or 0.3 to 0.6 μm.

The light-scattering particles may contain at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconia, zinc oxide, calcium carbonate, barium sulfate, and silica.

The surface tension of the ink composition may be 20 to 40 mN / m.

The viscosity of the ink composition can be 2 ~ 20mPa‧s.

The ink composition may further contain a solvent having a boiling point of 180 ° C or higher.

The ink composition can be used in a color filter.

The ink composition may be an ink composition (inkjet ink) used by an inkjet method.

One aspect of the present invention relates to a light conversion layer including a plurality of pixel portions having a pixel portion including a hardened body of the ink composition. The light conversion layer can reduce light leakage in the pixel portion.

The light conversion layer may further include a light-shielding portion provided between the plurality of pixel portions. The plurality of pixel portions may include a first pixel portion containing the above-mentioned hardened material and containing light having a wavelength in a range of 420 to 480 nm. Luminous nanocrystalline particles having light with a peak emission wavelength in the range of 605 to 665nm are used as the luminescent nanocrystalline particles; and the second pixel portion contains the above-mentioned hardened substance and contains light having a wavelength in a range of 420 to 480nm. Luminescent nanocrystalline particles that emit light having a peak emission wavelength in the range of 500 to 560nm are referred to as luminous nanocrystalline particles.

The plurality of pixel portions may further include a third pixel portion having a transmittance of 30% or more for light having a wavelength in a range of 420 to 480 nm.

One aspect of the present invention relates to a color filter including the light conversion layer. With this color filter, light leakage in the pixel portion can be reduced.

According to the present invention, an ink composition capable of reducing light leakage, and a light conversion layer and a color filter using the ink composition can be provided.

10‧‧‧pixel section

10a‧‧‧1st pixel section

10b‧‧‧ 2nd pixel section

10c‧‧‧The third pixel section

11a‧‧‧The first luminous nanocrystalline particle

11b‧‧‧Second luminescent nanocrystalline particle

12a‧‧‧1st light scattering particle

12b‧‧‧ 2nd light scattering particle

13a‧‧‧The first hardening ingredient

13b‧‧‧ 2nd hardening ingredient

13c‧‧‧3rd hardening ingredient

20‧‧‧Shading Department

30‧‧‧light conversion layer

40‧‧‧ substrate

100‧‧‧ color filter

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

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

<Ink composition>

An ink composition according to an embodiment includes light-emitting nanocrystalline particles, light-scattering particles, a photopolymerizable compound, and / or a thermosetting resin. The ink composition according to one embodiment is an ink composition for a color filter, and is used to form a pixel portion of a color filter by, for example, a photolithography method or an inkjet method.

The ink composition according to one embodiment is preferably used for forming a color filter pixel portion by an inkjet method. When a conventional ink composition is used to form a pixel portion of a color filter by an inkjet method, it is difficult to reduce light leakage from the pixel portion. On the other hand, according to the ink composition of the embodiment, even if it is an inkjet method, a pixel portion having an excellent light leakage reduction effect can be obtained.

Hereinafter, the ink composition for color filters (inkjet inks for color filters) used for an inkjet system is demonstrated as an example.

[Luminescent nanocrystalline particles]

The light-emitting nanocrystalline particles are nano-sized crystals that absorb fluorescence and emit fluorescence or phosphorescence, and are, for example, crystals having a maximum particle diameter of 100 nm or less as measured by a transmission electron microscope or a scanning electron microscope.

The luminescent nanocrystalline particles can emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength by absorbing light of a specific wavelength, for example. The luminescent nanocrystalline particles may be red luminescent nanocrystal particles emitting light (red light) having a luminescent peak wavelength in the range of 605 to 665nm, or may be luminescent nanoparticle particles having a luminescent peak wavelength in the range of 500 to 560nm. The green luminescent nanocrystalline particles of light (green light) may also be blue luminescent nanocrystalline particles that emit light (blue light) having an emission peak wavelength in the range of 420 to 480 nm. In this embodiment, it is preferable that the ink composition contains at least one of the light-emitting nanocrystalline particles. The light absorbed by the luminescent nanocrystalline particles may be, for example, light (blue light) having a wavelength in a range of 400 nm to 500 nm or light (ultraviolet light) having a wavelength in a range of 200 nm to 400 nm. The emission peak wavelength of the luminescent nanocrystalline particles can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using an ultraviolet-visible spectrophotometer.

The red light-emitting nanocrystalline particles are preferably 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 has a light emission peak wavelength, and preferably has a light emission peak wavelength of 628 nm or more, 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more, 610 nm or more, 607 nm or more, or 605 nm or more. These upper and lower limits can be arbitrarily combined. In addition, in the same description below, the upper limit value and the lower limit value may be individually arbitrarily combined.

Green luminous nanocrystalline particles preferably have emission peaks below 560nm, 557nm, 555nm, 550nm, 547nm, 545nm, 543nm, 540nm, 537nm, 535nm, 532nm or 530nm. The wavelength is preferably 528 nm or more, 525 nm or more, 523 nm or more, 520 nm or more, 515 nm or more, 510 nm or more, 507 nm or more, 505 nm or more, 503 nm or more, or 500 nm or more.

The blue luminescent nanocrystalline particles preferably emit light at 480 nm, 477 nm, 475 nm, 470 nm, 467 nm, 465 nm, 463 nm, 460 nm, 457 nm, 455 nm, 452 nm, or 450 nm. The peak wavelength preferably has an emission peak wavelength of 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.

Regarding the wavelength (luminous color) of the light emitted by the luminescent nanocrystalline particles, according to the solution of the Schrodinger wave equation of the square-well potential model, it depends on the luminescent nanometer The size (eg, particle size) of the crystalline particles also depends on the energy gap of the luminescent nanocrystalline particles. Therefore, the emission color can be selected by changing the material and size of the luminescent nanocrystal particles used.

The luminescent nanocrystalline particles may be luminescent nanocrystalline particles (luminescent semiconductor nanocrystalline particles) containing a semiconductor material. Examples of the light-emitting semiconductor nanocrystalline particles include quantum dots (hereinafter also referred to as "QD"), quantum rods, and the like. Among these, quantum dots are preferred from the viewpoints that it is easy to control the light emission spectrum, ensure reliability, reduce production costs, and improve mass productivity.

The light-emitting semiconductor nanocrystalline particles may be composed only of a core containing a first semiconductor material, or may include at least a core containing a first semiconductor material, and at least a core containing a second semiconductor material different from the first semiconductor material and covering the core. Part of the shell. In other words, the structure of the light-emitting semiconductor nanocrystalline particles may be a structure consisting of only a core (core structure), or a structure consisting of a core and a shell (core / shell structure). In addition, the light-emitting semiconductor nanocrystalline particles may further include a third semiconductor material different from the first and second semiconductor materials and cover at least a portion of the core, in addition to the case (first shell) of the second semiconductor material. Shell (second shell). In other words, the structure of the light-emitting semiconductor nanocrystalline particles may be a structure (core / shell / shell structure) composed of a core, a first shell, and a second shell. Each core and shell may be a mixed crystal containing two or more semiconductor materials (for example, CdSe + CdS, CIS + ZnS, etc.).

The luminescent nanocrystalline particles are preferably contained in a group selected from the group consisting of a group II-VI semiconductor, a group III-V semiconductor, a group I-III-VI semiconductor, a group IV semiconductor, and a group I-II-IV-VI semiconductor. At least one semiconductor material is used as the semiconductor material.

Specific semiconductor materials include: CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe , CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeAs, AlGaSP, AlGaP, AlGaP , InP, InAs, InSb, GaNP, GaAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNP, , GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, PbSe, PbSe, PbSe, PbSTe, PbST , SnPbSTe; Si, Ge, SiC , SiGe, AgInSe 2, CuGaSe 2, CuInS 2, CuGaS 2, CuInSe 2, AgInS 2, AgGaSe 2, AgGaS 2, C, Si and Ge. From the viewpoint of easy control of the emission spectrum of the light-emitting semiconductor nanocrystalline particles, ensuring reliability, reducing production costs, and improving mass productivity, it is preferable to contain a material selected from the group consisting of 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, At least one of the group consisting of CuGaSe ₂ , CuGaTe ₂ , Si, C, Ge, and Cu ₂ ZnSnS ₄ .

Examples of the red light-emitting semiconductor nanocrystalline particles include CdSe nanocrystalline particles, CdSe rod-like nanocrystalline particles, a core-shell structure, the shell portion being CdS, and the inner core portion being CdSe. Rod-shaped nanocrystalline particles, rod-shaped nanocrystalline particles having a core-shell structure and the shell portion being CdS and the inner core portion being ZnSe, rod-like nanocrystalline particles having a core-shell structure and the shell portion being CdS and the inner core portion being Nanocrystalline particles of CdSe, nanocrystalline particles with a core-shell structure, the shell part of which is CdS, and the inner core part is ZnSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, and mixed rods of CdSe and ZnS Nanocrystalline particles of the shape, Nanocrystalline particles of the InP, Nanocrystalline particles of the InP, Nanocrystalline particles of the rod shape of the InP, Nanocrystalline particles of the mixed crystal of CdSe and CdS, Mixed crystals of the CdSe and CdS Rod-shaped nanocrystalline particles, ZnSe and CdS mixed crystal nanocrystalline particles, ZnSe and CdS mixed crystal rod-like nanocrystalline particles, and the like.

Examples of green nanocrystalline semiconductor particles include nanocrystalline particles of CdSe, nanocrystalline particles of rod shape of CdSe, nanocrystalline particles of mixed crystal of CdSe and ZnS, and mixed crystals of CdSe and ZnS. The rod-like nanocrystalline particles.

Examples of the blue light-emitting semiconductor nanocrystalline particles include nanocrystalline particles of ZnSe, nanocrystalline particles of rod shape of ZnSe, nanocrystalline particles of ZnS, nanocrystalline particles of rod of ZnS, Nanocrystalline particles having a core-shell structure and the shell portion being ZnSe and the inner core portion being ZnS, rod-shaped nanocrystalline particles having a core-shell structure and the shell portion being ZnSe and the inner core portion being ZnS, CdS Nanocrystalline particles, rod-like nanocrystalline particles of CdS, and the like. Under the same chemical composition, semiconductor nanocrystalline particles can change the color that should be emitted by the particles to red or green by changing their average particle size. In addition, the semiconductor nanocrystalline particles are preferably those whose adverse effects on the human body and the like are as low as possible. In the case of using semiconductor nanocrystalline particles containing cadmium, selenium, etc. as the luminous nanocrystalline particles, it is preferable to select semiconductor nanocrystalline particles that do not contain the above elements (cadmium, selenium, etc.) as much as possible and use them alone, or Used in combination with other luminescent nanocrystalline particles to minimize the above elements.

The shape of the luminescent nanocrystalline particles is not particularly limited, and may be an arbitrary geometric shape or an arbitrary irregular shape. The shape of the light-emitting nanocrystalline particles may be, for example, a spherical shape, an elliptical shape, a pyramid shape, a dish shape, a branch shape, a mesh shape, or a rod shape. However, from the viewpoint of further improving the uniformity and fluidity of the ink composition, it is preferable to use, as the luminescent nanocrystalline particles, particles having a particle shape and less directivity (for example, spherical, regular four sides). Body-like particles).

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

From the viewpoint of dispersion stability, the luminescent nanocrystalline particles preferably have an organic ligand on the surface. The organic ligand may be bonded to the surface of the luminescent nanocrystalline particle, for example. In other words, the surface of the luminescent nanocrystalline particles can be passivated by an organic ligand. When the ink composition further contains a polymer dispersant described below, the luminescent nanocrystalline particles may have a polymer dispersant on the surface thereof. In this embodiment, for example, an organic ligand can be removed from the above-mentioned luminescent nanocrystalline particles having an organic ligand, and the organic ligand can be exchanged with a polymer dispersant to thereby bond the polymer dispersant. On the surface of luminescent nanocrystalline particles. However, from the viewpoint of dispersion stability when the inkjet ink is made, it is preferable that a polymer dispersant is blended with the luminescent nanocrystalline particles in a state in which an organic ligand is coordinated.

Examples of the organic ligand include TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine, trioctylamine, cetylamine, and octane Alcohol, dodecanethiol, hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA).

As the light-emitting nanocrystalline particles, those dispersed in an organic solvent, a photopolymerizable compound, or the like in a colloidal form can be used. The surface of the luminescent nanocrystalline particles in a dispersed state in an organic solvent is preferably passivated by the organic ligand. Examples of the organic solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, naphthalene, diphenyl ether, propylene glycol monomethyl ether acetate, and butylcarbitol acetate. Esters, or mixtures of these.

As the light-emitting nanocrystalline particles, a commercially available product can be used. Examples of commercially available products of the luminescent nanocrystalline particles include indium phosphide / zinc sulfide, D-dots, CuInS / ZnS from NN-Labs, and InP / ZnS from Aldrich.

The content of the light-emitting nanocrystalline particles may be 5 mass% or more, or 10 mass% or more based on the mass of the non-volatile component of the ink composition from the viewpoint that the light leakage reduction effect is more excellent. It is 15 mass% or more, 20 mass% or more, 30 mass% or more, and 40 mass% or more. The content of the luminescent nanocrystalline particles may be 70% by mass or less, or 60% by mass or less, based on the mass of the non-volatile component of the ink composition as a reference. It may be 50% by mass or less. In addition, in this specification, the "mass of the non-volatile component of the ink composition" refers to the mass obtained by removing the mass of the solvent from the total mass of the ink composition when the ink composition contains a solvent. When the ink composition contains no solvent, it refers to the total mass of the ink composition.

[Light scattering particles]

The light-scattering particles are, for example, optically inactive inorganic fine particles. The light-scattering particles scatter light from a light source that is irradiated to the pixel portion of the color filter.

Examples of the material constituting the light-scattering particles include elemental metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; silicon dioxide, barium sulfate, barium carbonate, and calcium carbonate , Talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, aluminum white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconia, zinc oxide and other metal oxides; magnesium carbonate, Metal carbonates such as barium carbonate, bismuth hypocarbonate, calcium carbonate; metal hydroxides such as aluminum hydroxide; composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate, and bismuth hyponitrate And other metal salts. The light-scattering particles preferably contain at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconia, zinc oxide, calcium carbonate, barium sulfate, and silicon dioxide from the viewpoint that the light leakage reduction effect is more excellent. One type, more preferably at least one selected from the group consisting of titanium oxide, barium sulfate, and calcium carbonate.

The shape of the light-scattering particles may be spherical, filamentous, or irregular. However, in terms of further improving the uniformity, fluidity, and light scattering properties of the ink composition, as the light scattering particles, it is preferable to use particles having a particle shape and less directivity (for example, spherical, Regular tetrahedron-like particles).

The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 0.05 μm or more, may be 0.2 μm or more, and may be 0.3 μm or more from the viewpoint that the light leakage reduction effect is more excellent. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 1.0 μm or less, may be 0.6 μm or less, and may be 0.4 μm or less in terms of excellent ejection stability. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 0.05 to 1.0 μm, 0.05 to 0.6 μm, 0.05 to 0.4 μm, 0.2 to 1.0 μm, 0.2 to 0.6 μm, 0.2 to 0.4 μm, 0.3 to 1.0 μm, 0.3 to 0.6 μm, or 0.3 to 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 50 nm or more and 1,000 nm or less. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition can be obtained by measuring with a dynamic light scattering-type Nanotrac particle size distribution meter and calculating the volume average diameter. The average particle diameter (volume average diameter) of the light-scattering particles used can be obtained by measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope, and calculating the volume average diameter.

The content of the light-scattering particles can be 0.1 mass% or more, or 1 mass% or more, based on the mass of the non-volatile component of the ink composition, from the standpoint that the light leakage reduction effect is more excellent. It may be 7 mass% or more, 10 mass% or more, or 12 mass% or more. The content of the light-scattering particles may be 60% by mass or less based on the mass of the non-volatile component of the ink composition from the viewpoint of more excellent light leakage reducing effect and excellent ejection stability. It may be 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, and 15% by mass or less. In this embodiment, since the ink composition contains a polymer dispersant, the light-scattering particles can be dispersed well even when the content of the light-scattering particles is in the above range.

The mass ratio of the content of the light-scattering particles to the content of the light-emitting nanocrystalline particles (light-scattering particles / light-emitting nanocrystalline particles) may be 0.1 or more from the viewpoint that the light leakage reduction effect is more excellent, It may be 0.2 or more, and may be 0.5 or more. The mass ratio (light-scattering particles / light-emitting nanocrystalline particles) may be 5.0 or less, or 2.0 or less, from the viewpoint of better light leakage reduction effect and excellent continuous ejection performance during inkjet printing. It is 1.5 or less. In addition, it is considered that the light leakage reduction by the light-scattering particles is based on the following mechanism. That is, it is considered that when there is no light-scattering particle, the light of the backlight only passes straight through the pixel portion, and there is less chance of being absorbed by the light-emitting nanocrystalline particles. On the other hand, if the light-scattering particles and the luminescent nanocrystalline particles exist in the same pixel portion, the light of the backlight is scattered in all directions in the pixel portion, and the luminescent nanocrystalline particles can receive the light of the backlight. Therefore, even if the same backlight is used, the amount of light absorption in the pixel portion is expected to increase. As a result, it is thought that light leakage can be prevented by this mechanism.

[Photopolymerizable compound]

The photopolymerizable compound of this embodiment is a photoradically polymerizable compound or a photocationic polymerizable compound that is polymerized by irradiation of light, and may be a photopolymerizable monomer or oligomer. These can be used together with a photopolymerization initiator. The photo radical polymerizable compound can be used together with the photo radical polymerization initiator, and the photo cationic polymerizable compound can be used together with the photo cationic polymerization initiator. In other words, the ink composition may include a photopolymerizable component including a photopolymerizable compound and a photopolymerization initiator, and may also include a photoradical polymerization property including a photoradical polymerizable compound and a photoradical polymerization initiator. The component may contain a photocationically polymerizable component including a photocationically polymerizable compound and a photocationic polymerization initiator. A photoradical polymerizable compound and a photocationically polymerizable compound may be used in combination, a compound having photoradical polymerizability and photocationic polymerizability may be used, or a photoradical polymerization initiator and a photocationic polymerization initiator may be used in combination. The photopolymerizable compound may be used singly or in combination of two or more kinds.

Examples of the photoradically polymerizable compound include a (meth) acrylate compound. The (meth) acrylate compound may be a monofunctional (meth) acrylate having one (meth) acrylfluorenyl group, or a polyfunctional (meth) acrylate having a plurality of (meth) acrylfluorenyl groups. . From the viewpoint of excellent fluidity at the time of ink formation, the viewpoint of more excellent ejection stability, and the viewpoint of suppressing a decrease in smoothness due to curing shrinkage during the manufacture of a color filter, it is preferable to use a monofunctional combination (Meth) acrylates and polyfunctional (meth) acrylates. In addition, in this specification, (meth) acrylate means "acrylate" and the corresponding "methacrylate". The expression "(meth) acrylfluorenyl" is also the same.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) Amyl acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate Alkyl ester, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) Phenoxyethyl acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate Ethyl ester, isoamyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, (meth) acrylate 2 -Hydroxy-3-phenoxypropyl ester, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylbenzyl (meth) acrylate, Succinic acid mono (2-propenyloxy Ethyl), N- [2- (propenyloxy) ethyl] phthalimide, N- [2- (propenyloxy) ethyl] tetrahydrophthalimide Wait.

The polyfunctional (meth) acrylate may be a bifunctional (meth) acrylate, a trifunctional (meth) acrylate, a 4-functional (meth) acrylate, a 5-functional (meth) acrylate, or a 6-functional (meth) acrylate. (Meth) acrylate and the like, for example, two hydroxy groups of a diol compound may be substituted with (meth) acryloxy bis (meth) acrylates, and two or three hydroxy groups of a triol compound may be substituted with ( Meth) acrylic acid oxybis or tris (meth) acrylate.

Specific examples of the bifunctional (meth) acrylate include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5- Pentylene glycol 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, tricyclodecanedimethanol di (meth) acrylate Ester, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) 2 hydroxy groups of acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate diacrylate, and tris (2-hydroxyethyl) isocyanurate were replaced with (methyl) The two hydroxyl groups of propylene glycol di (meth) acrylate and diol obtained by adding 1 mol of neopentyl glycol to 4 mol or more of ethylene oxide or propylene oxide are substituted with (a Di) (meth) acrylic acid bis (meth) acrylate, 1 mol bisphenol A plus 2 mol of ethylene oxide or propylene oxide obtained from the two hydroxyl groups of the diol were replaced with (meth) acrylic alkoxy di (meth) acrylate, p-trimethylolpropane 1 mol Two hydroxy groups of triol obtained by adding ethylene oxide or propylene oxide of 3 mol or more are substituted with (meth) acryloxy bis (meth) acrylate, and 1 mol of bis Two hydroxy groups of a diol obtained by adding phenol A to ethylene oxide or propylene oxide of 4 mol or more are substituted with (meth) acryloxy bis (meth) acrylate and the like.

Specific examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, glycerol triacrylate, neopentyl alcohol tri (meth) acrylate, and p-trimethylol Three hydroxy groups of triol obtained by adding 1 mol of propane to 3 mol of ethylene oxide or propylene oxide are substituted with (meth) acrylic alkoxy tri (meth) acrylate and the like.

Specific examples of the tetrafunctional (meth) acrylate include neopentaerythritol tetra (meth) acrylate.

Specific examples of the pentafunctional (meth) acrylate include dipentaerythritol penta (meth) acrylate.

As a specific example of a 6-functional (meth) acrylate, a dipentaerythritol hexa (meth) acrylate is mentioned.

The polyfunctional (meth) acrylate may be a poly (meth) group in which multiple hydroxyl groups of dipentaerythritol such as dipentaerythritol hexa (meth) acrylate are substituted with (meth) acryloxy Acrylate.

The (meth) acrylate compound may be an ethylene oxide modified phosphate (meth) acrylate having a phosphate group, an ethylene oxide modified alkyl phosphate (meth) acrylate, or the like.

Examples of the photocationically polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether compound.

Examples of the epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac type epoxy compound, trimethylolpropane polyglycidyl ether, and neopentyl glycol diglycidyl ether. And other aliphatic epoxy compounds; 1,2-epoxy-4-vinylcyclohexane, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1. 0] Alicyclic epoxy compounds such as heptane and the like.

As the epoxy compound, a commercially available product may be used. As commercially available epoxy compounds, for example, "Celloxide 2000", "Celloxide 3000" and "Celloxide 4000" manufactured by Daicel Chemical Industry Co., Ltd. can be used.

Examples of the cationically polymerizable oxetane compound include 2-ethylhexyloxetane, 3-hydroxymethyl-3-methyloxetane, and 3-hydroxymethyl-3- Ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane, 3-hydroxymethyl-3-benzene Oxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxy Heterocyclobutane, 3-hydroxyethyl-3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane Butane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane , 3-hydroxybutyl-3-methyloxetane, and the like.

As the oxetane compound, a commercially available product can also be used. As commercially available products of the oxetane compound, for example, the ARONE OXETANE series ("OXT-101", "OXT-212", "OXT-121", "OXT-221") manufactured by Toa Synthesis Co., Ltd. can be used. ); "Celloxide 2021", "Celloxide 2021A", "Celloxide 2021P", "Celloxide 2080", "Celloxide 2081", "Celloxide 2083", "Celloxide 2085", "EPOLEAD GT300", "EPOLEAD GT301", "EPOLEAD GT302", "EPOLEAD GT400", "EPOLEAD GT401" and "EPOLEAD GT403"; "Cyracure UVR-6105", "Cyracure UVR-6107", "Cyracure UVR" manufactured by Dow Chemical Japan Co., Ltd. -6110 "," Cyracure UVR-6128 "," ERL4289 ", and" ERL4299 ". In addition, known oxetane compounds (for example, the oxetane compounds described in Japanese Patent Application Laid-Open No. 2009-40830 and the like) may 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.

In addition, as the photopolymerizable compound in this embodiment, the photopolymerizable compound described in paragraphs 0042 to 0049 of Japanese Patent Application Laid-Open No. 2013-182215 can also be used.

In the ink composition of this embodiment, when a hardenable component is constituted only with a photopolymerizable compound or a main component thereof, the durability (strength, heat resistance, etc.) of the hardened material can be further improved. More specifically, as the photopolymerizable compound as described above, it is more preferable to use a bifunctional or more polyfunctional photopolymerizable compound having two or more polymerizable functional groups in one molecule as an essential component.

The photopolymerizable compound may be alkali-insoluble from the viewpoint of easily obtaining a pixel portion of a color filter with excellent reliability. As used herein, the term “photopolymerizable compound is alkali-insoluble” means that the dissolved amount of the photopolymerizable compound at 25 ° C. with respect to a 1% by mass potassium hydroxide aqueous solution is 30% by mass or less based on the total mass of the photopolymerizable compound. . The above-mentioned dissolved amount of the photopolymerizable compound is preferably 10% by mass or less, and more preferably 3% by mass or less.

The content of the photopolymerizable compound makes it easy to obtain a suitable viscosity as an inkjet ink, the viewpoint that the curability of the ink composition becomes good, and the solvent resistance and abrasion resistance of the pixel portion (cured substance of the ink composition). From the viewpoint of improvement, based on the mass of the non-volatile component of the ink composition, it may be 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the photopolymerizable compound is from the viewpoint of easily obtaining a suitable viscosity as an inkjet ink, and from the viewpoint of obtaining more excellent optical characteristics (light leakage), based on the quality of the non-volatile component of the ink composition. It is 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, and 50% by mass or less.

The photopolymerizable compound may have a crosslinkable group from the viewpoint of excellent stability of the pixel portion (hardened material of the ink composition) (for example, suppression of deterioration with time, high-temperature storage stability, and wet heat storage stability). . The crosslinkable group is a functional group that reacts with other crosslinkable groups through heat or active energy rays (for example, ultraviolet rays). Examples include epoxy groups, oxetanyl groups, vinyl groups, and acrylic fluorene. Group, propylene alkoxy group, vinyl ether group and the like.

[Photo radical polymerization initiator]

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

As a molecular cleavage type photoradical polymerization initiator, benzoin isobutyl ether, 2,4-diethyl-9-oxosulfur can be suitably used. , 2-isopropyl-9-oxysulfur , 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one Bis (2,6-dimethoxybenzylidene) -2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzylidene) ethoxybenzene Based phosphine oxide, etc. As a photo-radical polymerization initiator other than the above-mentioned molecular cleavage type, 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzoin dimethyl ketal, 2-hydroxy-2-methyl- 1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, and 2-methyl-1- (4-methylthiobenzene ) -2-morpholinylpropan-1-one.

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

[Photocationic polymerization initiator]

Examples of the photocationic polymerization initiator include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; diphenylsulfonium hexafluoroantimonate and p-nonyl Polyarylphosphonium salts such as phenylphosphonium hexafluoroantimonate and the like.

As the photocationic polymerization initiator, a commercially available product may be used. Examples of commercially available products include sulfonium-based photocationic polymerization initiators such as "CPI-100P" manufactured by San-Apro Corporation, fluorenyl phosphine oxide compounds such as "Lucirin TPO" manufactured by BASF Corporation, and "fluorene-based phosphine oxide compounds manufactured by BASF Corporation" "Irgacure 907", "Irgacure 819", "Irgacute 379EG", "Irgacure 184", "Irgacure PAG290", etc.

The content of the photopolymerization initiator may be 0.1 part by mass or more with respect to 100 parts by mass of the photopolymerizable compound, or 0.5 part by mass or more with respect to 100 parts by mass of the photopolymerizable compound. the above. The content of the photopolymerization initiator may be 40 parts by mass or less, and may be 30 parts by mass based on 100 parts by mass of the photopolymerizable compound from the viewpoint of the stability of the hydroxy group of the pixel portion (the cured product of the ink composition). It may be 20 parts by mass or less.

[Thermosetting resin]

In this embodiment, the so-called thermosetting resin is a resin which functions as a binder in a cured material and is crosslinked and cured by heat. The thermosetting resin has a curable group. Examples of the curable group include an epoxy group, an oxetanyl group, an isocyanate group, an amine group, a carboxyl group, and a methylol group. From the viewpoint of being excellent in heat resistance and storage stability of a cured product of the ink composition, and From the viewpoint of excellent adhesion between the light-shielding portion (for example, a black matrix) and the substrate, an epoxy group is preferred. The thermosetting resin may have one type of curable group or two or more types of curable group.

Furthermore, the thermosetting resin contains a resin having photoradical polymerizability (polymerized by irradiation with light when used together with a photoradical polymerization initiator) and a photocationic polymerizability ( (When used together with a photocationic polymerization initiator, the resin is polymerized by irradiation with light). When the ink composition contains a photo-radical polymerizable thermosetting resin and a photo-radical polymerization initiator, the photo-radical polymerizable thermosetting resin is classified as a photo-radical polymerizable compound ( Photopolymerizable compound). When the ink composition contains a photocationically polymerizable thermosetting resin and a photocationic polymerization initiator, the photocationically polymerizable thermosetting resin is classified as a photocationically polymerizable compound (photopolymerizable compound). ).

The thermosetting resin may be a polymer (homopolymer) of a single monomer or a copolymer of a plurality of monomers. 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 functional groups in one molecule can be used, and it is usually used in combination with a curing agent. When a thermosetting resin is used, a catalyst (hardening accelerator) that can accelerate the thermosetting reaction may be further added. In other words, the ink composition may contain a thermosetting component containing a thermosetting resin (and a hardening agent and a hardening accelerator, if necessary). In addition to these, a polymer having no polymerization reactivity in itself may be further used.

As a compound having two or more thermosetting functional groups in one molecule, for example, an epoxy resin having two or more epoxy groups in one molecule (hereinafter also referred to as a "multifunctional epoxy resin") can be used. "Epoxy resin" includes both monomeric epoxy resins and polymeric epoxy resins. The number of epoxy groups in one molecule of the multifunctional epoxy resin is preferably 2 to 50, more preferably 2 to 20. The epoxy group may have a structure having an ethylene oxide ring structure, and may be, for example, glycidyl, oxyethyl, cyclohexyl, or the like. Examples of the epoxy resin include a well-known multivalent epoxy resin that can be cured by a carboxylic acid. Such epoxy resins have been widely disclosed in, for example, the "Polyepoxy Handbook" edited by Shinbo Masaki, and the Industrial News Agency (1987), etc., and these can be used.

Examples of the thermosetting resin (including polyfunctional epoxy resin) having an epoxy group include polymers of monomers having an ethylene oxide ring structure, monomers having an ethylene oxide ring structure, and other monomers. Copolymer. Specific examples of the polyfunctional epoxy resin include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, N-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl methacrylate) ) Methyl ester-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate, and the like. In addition, as the thermosetting resin of the present embodiment, the compounds described in paragraphs 0044 to 0066 of Japanese Patent Application Laid-Open No. 2014-56248 can also be used.

As the polyfunctional epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, and diphenyl ether can be used. Epoxy resin, hydroquinone epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fluorene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin , Trihydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenol ethane epoxy resin, dicyclopentadienephenol epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol A core-containing polyol epoxy resin, polypropylene glycol epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, glyoxal epoxy resin, alicyclic epoxy resin, heterocyclic ring Type epoxy resin and so on.

More specifically, examples include a bisphenol A type epoxy resin such as the trade name "EPIKOTE 828" (manufactured by Japan Epoxy Resins), and a bisphenol F type epoxy resin such as the trade name "YDF-175S" (manufactured by Toto Kasei Corporation). Resin, brominated bisphenol A type epoxy resin such as trade name "YDB-715" (manufactured by Toto Kasei Co., Ltd.), bisphenol S type epoxy resin such as trade name "EPICLON EXA1514" (manufactured by DIC Corporation), trade name Hydroquinone-type epoxy resins such as `` YDC-1312 '' (manufactured by Toto Kasei Co., Ltd.), trade names `` EPICLON EXA4032 '', `` HP-4770 '', `` HP-4700 '', and `` HP-5000 '' (DIC Corporation) (Manufactured) and other naphthalene-type epoxy resins, biphenyl type epoxy resin under the trade name "EPIKOTE YX4000H" (manufactured by Japan Epoxy Resins), and bisphenol A-type novolak resin under the trade name "EPIKOTE 157S70" (manufactured by Japan Epoxy Resins) Epoxy resin, phenol novolac-type epoxy resin with trade name "EPIKOTE 154" (manufactured by Japan Epoxy Resins), trade name "YDPN-638" (manufactured by Tohto Kasei Co., Ltd.), trade name "YDCN-701" (Tohto (Manufactured by Kasei Corporation) and other cresol novolac epoxy resins , Dicyclopentadiene phenol-type epoxy resins under the trade names "EPICLON HP-7200", "HP-7200H" (manufactured by DIC Corporation), and trihydroxys under the trade name "EPIKOTE 1032H60" (manufactured by Japan Epoxy Resins) Trifunctional epoxy resins such as phenylmethane type epoxy resin, trade name "VG3101M80" (manufactured by Mitsui Chemicals), and tetraphenol based epoxy resins such as "EPIKOTE 1031S" (manufactured by Japan Epoxy Resins) Hydrogenated bisphenol A epoxy resin, such as 4-functional epoxy resin under the trade name "DENACOL EX-411" (manufactured by Nagase ChemteX), "ST-3000" (manufactured by Toto Kasei Co., Ltd.), and the trade name "EPIKOTE" 190P "(made by Japan Epoxy Resins) and other glycidyl ester type epoxy resins, trade name" YH-434 "(manufactured by Toto Kasei Co., Ltd.) and other glycidylamine type epoxy resins, trade name" YDG-414 "(Toto Kasei Co., Ltd.) (Manufactured by the company) and other heterocyclic types such as glyoxal-type epoxy resin, alicyclic polyfunctional epoxy compounds such as "EPOLEAD GT-401" (manufactured by Daicel Chemical Co., Ltd.), and triglycidyl isocyanate (TGIC) Epoxy, etc. In addition, as the epoxy-reactive diluent, a brand name "Neotohto E" (manufactured by Toto Kasei Co., Ltd.) can be mixed as necessary.

As the polyfunctional epoxy resin, "FINEDIC A-247S", "FINEDIC A-254", "FINEDIC A-253", "FINEDIC A-229-30A", "FINEDIC" manufactured by DIC Corporation can be used. A-261 "," FINEDIC A249 "," FINEDIC A-266 "," FINEDIC A-241 "" FINEDIC M-8020 "," EPICLON N-740 "," EPICLON N-770 "," EPICLON N-865 " (Brand name) and so on.

As a thermosetting resin, if a polyfunctional epoxy resin having a relatively small molecular weight is used, an epoxy group is replenished in the ink composition (inkjet ink), and the reaction point concentration of the epoxy group becomes high, which can improve the cross-linking.联 质量。 The density.

Even in a polyfunctional epoxy resin, 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 functions) from the viewpoint of increasing the crosslinking density. In particular, when a thermosetting resin having a weight average molecular weight of 10,000 or less is used to improve the ejection stability via the ejection head in the inkjet method, the strength and hardness of the pixel portion (hardened product of the ink composition) tends to decrease. Therefore, from the viewpoint of sufficiently increasing the crosslinking density, it is preferred that a polyfunctional epoxy resin having four or more functions is blended in the ink composition (inkjet ink).

Examples of the hardening agent and hardening accelerator for hardening the thermosetting resin include 4-methylhexahydrophthalic anhydride, triethylenetriamine, diaminodiphenylmethane, and phenol novolac. Varnish resin, tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, triphenylphosphine, 3-phenyl-1,1- Dimethyl urea and so on.

The thermosetting resin may be alkali-insoluble from the viewpoint of easily obtaining a pixel portion of a color filter having excellent reliability. The term "thermosetting resin is alkali-insoluble" means that the amount of the thermosetting resin at 25 ° C dissolved in a 1% by mass potassium hydroxide aqueous solution is 30% by mass or less based on the total mass of the thermosetting resin. The dissolving amount of the thermosetting resin is preferably 10% by mass or less, and more preferably 3% by mass or less.

The weight-average molecular weight of the thermosetting resin makes it easy to obtain a viscosity suitable as an inkjet ink, a viewpoint that the curability of the ink composition becomes good, a solvent resistance of the pixel portion (cured substance of the ink composition), and From the viewpoint of improving abrasion resistance, it may be 750 or more, 1,000 or more, or 2,000 or more. From the viewpoint of setting an appropriate viscosity as an inkjet ink, it 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.

The content of the thermosetting resin makes it easy to obtain a suitable viscosity as an inkjet ink, the viewpoint that the curability of the ink composition becomes good, and the solvent resistance and abrasion resistance of the pixel portion (cured substance of the ink composition). From the viewpoint of improvement, based on the mass of the non-volatile component of the ink composition, it may be 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the thermosetting resin is from the viewpoint that the viscosity of the inkjet ink does not become too high, and the thickness of the pixel portion is not too thick with respect to the light conversion function. It is 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, and 50% by mass or less.

In this embodiment, the ink composition may contain at least one of a photopolymerizable compound and a thermosetting resin, and may also contain both a photopolymerizable compound and a thermosetting resin. When the ink composition contains a photopolymerizable compound, it may not contain a thermosetting resin. When the ink composition contains a thermosetting resin, it may not contain a photopolymerizable compound. From the viewpoints of storage stability of an ink composition containing luminescent nanocrystalline particles (for example, quantum dots) and durability (humidity stability, etc.) of a pixel portion (hardened material of the ink composition), photopolymerization Among the compounds and thermosetting resins, it is preferable to use thermosetting resins for storage stability of the ink composition containing luminescent nanocrystalline particles (for example, quantum dots), and being less susceptible to heating by quantum dots From the viewpoint of curing at a deteriorated low temperature, it is more preferable to use a photoradically polymerizable compound to form a pixel portion (hardened product of ink composition) without being hindered by oxygen in the curing process. It is preferable to use a photocationically polymerizable compound.

When the ink composition contains a photopolymerizable compound and a thermosetting resin, the total content of the photopolymerizable compound and the thermosetting resin makes it easy to obtain a suitable viscosity as an inkjet ink, and curing of the ink composition From the viewpoint of improving the properties and improving the solvent resistance and abrasion resistance of the pixel portion (cured material of the ink composition), the mass of the nonvolatile component of the ink composition may be used as a reference, and may be 3% by mass or more. It can also be 5 mass% or more, 10 mass% or more, 15 mass% or more, and 20 mass% or more. In addition, in terms of the total content of the photopolymerizable compound and the thermosetting resin, the viscosity of the inkjet ink does not become too high, and the thickness of the pixel portion is not too thick with respect to the light conversion function. As a reference, the mass of the non-volatile component may be 80% by mass or less, 60% by mass or less, and 50% by mass or less.

The ink composition of this embodiment can be used as an ink for a known and commonly used method for manufacturing a color filter, so that relatively expensive materials such as luminescent nanocrystalline particles, solvents, etc. are not wasted in vain, and only used for a desired portion In terms of forming the color filter pixel portion (light conversion layer) in a required amount, it is preferably prepared and used in a manner more suitable for the inkjet method than the photolithography method. .

The viscosity of the ink composition may be, for example, 2 mPa · s or more, 5 mPa · s or more, or 7 mPa · s or more in terms of ejection stability during inkjet printing. The viscosity of the ink composition may be 20 mPa · s or less, 15 mPa · s or less, or 12 mPa · s or less. When the viscosity of the ink composition is 2 mPa · s or more, since the meniscus shape of the ink composition at the front end of the ink ejection hole of the ejection head is stable, it becomes easy to control the ejection of the ink composition (for example, controlling the ejection amount And when it spouts). On the other hand, when the viscosity is 20 mPa · s or less, the ink composition can be smoothly ejected from the ink ejection hole. The viscosity of the ink composition can also be 2 ~ 20mPa‧s, 2 ~ 15mPa‧s, 2 ~ 12mPa‧s, 5 ~ 20mPa‧s, 5 ~ 15mPa‧s, 2 ~ 20mPa‧s, 7 ~ 15mPa‧s, 7 ~ 12mPa‧s, or 7 ~ 12mPa‧s. The viscosity of the ink composition can be measured by, for example, an E-type viscometer.

The surface tension of the ink composition is preferably a surface tension suitable for the inkjet method, specifically, a range of 20 to 40 mN / m is preferable, and a range of 25 to 35 mN / m is more preferable. By setting the surface tension to this range, occurrence of flight deviation can be suppressed. In addition, the so-called flying deviation means that when the ink composition is ejected from the ink ejection hole, the position where the ink composition is applied is shifted from the target position by 30 μm or more. When the surface tension is 40 mN / m or less, since the shape of the meniscus at the front end of the ink ejection hole is stable, it becomes easy to control the ejection of the ink composition (for example, controlling the ejection amount and the timing of ejection). On the other hand, when the surface tension is 20 mN / m or less, the occurrence of flight deviation can be suppressed. That is, there is no case where a pixel portion where ink composition is insufficiently filled is not accurately sprayed to a pixel portion formation area to be sprayed, or an ink composition is sprayed to a pixel portion formation area to be sprayed. Adjacent pixel portions form regions (or pixel portions), and color reproducibility decreases.

The ink composition may further contain light-emitting nanocrystalline particles, light-scattering particles, photopolymerizable compounds, thermosetting resins, polymerization initiators, and organic ligands as long as the effects of the present invention are not hindered. ingredient. Examples of the other components include a polymer dispersant, a sensitizer, and a solvent.

[Polymer dispersant]

In the present invention, the polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having affinity for light scattering particles, and has a function of dispersing the light scattering particles. The polymer dispersant is adsorbed on the light-scattering particles through a functional group having an affinity for the light-scattering particles, and the light-scattering particles are dispersed in the ink composition by electrostatic repulsion and / or steric repulsion of the polymer dispersants. in. The polymer dispersant is preferably bound to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may also be adsorbed to the surface of the light-emitting nanocrystalline particles and adsorbed to the light-emitting nanoparticle, and may also be composed of ink.中 Free.

However, when a conventional ink composition is used to form a color filter pixel portion by an inkjet method, there is a discharge stability from an inkjet nozzle due to agglomeration of luminous nanocrystalline particles and light scattering particles, and the like. Reduced situation. In addition, it is thought that by miniaturizing the light-emitting nanocrystalline particles and light-scattering particles, and reducing the content of the light-emitting nanocrystalline particles and light-scattering particles, the discharge stability is improved. It is easy to reduce the reduction effect, and it is difficult to achieve both the sufficient discharge stability and the reduction effect of light leakage. In contrast, according to the ink composition further containing a polymer dispersant, light leakage can be further reduced while ensuring sufficient ejection stability. The reason why such an effect is obtained is not clear, but it is presumed that the aggregation of the luminescent nanocrystalline particles and the light-scattering particles (especially the light-scattering particles) is significantly suppressed by the polymer dispersant.

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. Acidic functional groups have dissociative protons and can be neutralized by bases such as amines and hydroxide ions. Basic functional groups can be neutralized by acids such as organic acids and inorganic acids.

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 amine groups, ammonium groups, imine groups, and pyridine, pyrimidine, and pyridine , Imidazole, triazole and other nitrogen-containing heterocyclic groups.

Examples of the nonionic functional group include a hydroxyl group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO _2- ), a carbonyl group, a methyl group, an ester group, and a carbonate. Group, amido, carbamoyl, ureido, thioamido, thiourea, sulfamolyl, cyano, alkenyl, alkynyl, phosphine oxide, phosphine sulfide.

From the viewpoint of the dispersion stability of the light-scattering particles, the viewpoint that the side effects of the precipitation of the luminescent nanocrystalline particles are unlikely to occur, the viewpoint of the ease of synthesis of the polymer dispersant, and the viewpoint of the stability of the functional group, As the acidic functional group, a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphate group can be preferably used, and as the basic functional group, an amine group can be preferably used. Among these, a carboxyl group, a phosphonic acid group, and an amine group are more preferably used, and an amine group is most preferably used.

The 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 1 to 150 mgKOH / g in terms of solid content conversion. When the acid value is 1 or more, it is easy to obtain sufficient dispersibility of the light-scattering particles. When the acid value is 150 or less, the storage stability of the pixel portion (hardened product of the ink composition) is not easily reduced.

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 1 to 200 mgKOH / g in terms of solid content. When the amine value is 1 or more, it is easy to obtain sufficient dispersibility of the light-scattering particles. When the amine value is 200 or less, the storage stability of the pixel portion (hardened product of the ink composition) is not easily reduced.

The polymer dispersant may be a polymer (homopolymer) of a single monomer or a copolymer of a plurality of monomers. 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 may be, for example, acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amine resin, polyethylen Polyamines such as imines and polyallylamines, epoxy resins, polyimide and the like.

As the above-mentioned polymer dispersant, a commercially available product may be used. As the commercially available product, AJISPER PB series of Ajinomoto Fine-Techno Co., Ltd., DISPERBYK series and BYK-series by BYK, and Efka series by BASF may be used Wait.

As commercially available products, for example, "DISPERBYK-130", "DISPERBYK-161", "DISPERBYK-162", "DISPERBYK-163", "DISPERBYK-164", "DISPERBYK-166" manufactured by BYK-Chemie can be used. , "DISPERBYK-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 "," DISPERBYK-2009 "," DISPERBYK-2020 "," DISPERBYK-2022 "," DISPERBYK- 2025, "DISPERBYK-2050", "DISPERBYK-2070", "DISPERBYK-2096", "DISPERBYK-2150", "DISPERBYK-2155", "DISPERBYK-2163", "DISPERBYK-2164", "BYK-LPN21116" And "BYK-LPN6919"; "EFKA4010", "EFKA4015", "EFKA4046", "EFKA4047", "EFKA4061", "EFKA4080", "EFKA4300", "EFKA4310", "EFKA4320", "EFKA4330" manufactured by BASF , "EFKA4340", "EFKA4560", "EFKA4585", "EFKA5207", "EFKA1501", "EFKA1502", "EFKA1503", and "EFKA PX-4701"; "SOLSPERSE 3000", "SOLSPERSE 9000", "SOLSPERSE 13240", "SOLSPERSE 13650", "SOLSPERSE 13650", manufactured by Lubrizol "SOLSPERSE 13940", "SOLSPERSE 11200", "SOLSPERSE 13940", "SOLSPERSE 16000", "SOLSPERSE 17000", "SOLSPERSE 18000", "SOLSPERSE 20000", "SOLSPERSE 21000", "SOLSPERSE 24000", "SOLSPERSE 26000", "SOLSPERSE 27000", "SOLSPERSE 28000", "SOLSPERSE 32000", "SOLSPERSE 32500", "SOLSPERSE 32550", "SOLSPERSE 32600", "SOLSPERSE 33000", "SOLSPERSE 34750", "SOLSPERSE 35100", "SOLSPERSE 35200", "SOLSPERSE 36000", "SOLSPERSE 37500", "SOLSPERSE 38500", "SOLSPERSE 39000", "SOLSPERSE 41000", "SOLSPERSE 54000", "SOLSPERSE 71000" and "SOLSPERSE 76500"; "Ajinomoto Fine-Techno Co., Ltd." AJISPER PB821 "," AJISPER PB822 "," AJISPER PB 881 "," PN411 "and" PA111 ";" TEGO Dispers650 "," TEGO Dispers660C "," TEGO Dispers662C "," TEGO Dispers670 "," TEGO Dispers685 "," TEGO Dispers700 "," TEGO Dispers710 "and" TEGO Dispers710 "manufactured by Evonik "TEGO Dispers760W"; "Disparlon DA-703-50", "DA-705" and "DA-725" manufactured by Kusumoto Chemicals.

As the polymer dispersant, in addition to the commercially available products described above, a cationic monomer containing a basic group and / or an anionic monomer having an acidic group, a monomer having a hydrophobic group, and if necessary, may be used. Other monomers (non-ionic monomers, monomers having a hydrophilic group, etc.) are copolymerized to synthesize the obtained ones. For 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 Japanese Patent Application Laid-Open No. 2004-250502 can be cited.

In addition, for example, a compound obtained by reacting a polyalkyleneimine with a polyester compound described in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Laid-Open No. 61-174939, and Japanese Patent No. The compound described in Kaiping No. 9-169821 modified with an amino group of a side chain of a polyallylamine polyester, and the polyester type macromonomer described in Japanese Unexamined Patent Publication No. 9-171253 as a copolymerization component Graft polymers, polyester polyol addition polyurethane described in Japanese Patent Application Laid-Open No. 60-166318, and the like.

The weight-average molecular weight of the polymer dispersant may be 750 or more, 1,000 or more, or 2,000 or more, from the viewpoint that the light-scattering particles can be well dispersed and the reduction effect of light leakage can be further improved. It is 3,000 or more. The weight-average molecular weight of the polymer dispersant can disperse the light-scattering particles well, can further improve the reduction effect of light leakage, and set the viscosity of the inkjet ink to a viscosity that can be ejected and suitable for stable ejection. It may be 100,000 or less, 50,000 or less, or 30,000 or less. In this specification, a weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by GPC (Gel Permeation Chromatography).

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, may be 2 parts by mass or more, and may be 5 parts by mass based on 100 parts by mass of the light-scattering particles. the above. The content of the polymer dispersant may be 50 parts by mass or less, and may be 30 parts by mass or less with respect to 100 parts by mass of the light-scattering particles, from the viewpoint of the moist heat stability of the pixel portion (the cured product of the ink composition). It may be 10 parts by mass or less.

[Sensitizer]

As the sensitizer, amines which do not undergo an addition reaction with a photopolymerizable compound and a thermosetting resin can be used. Examples of the sensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, p-dimethylaminobenzoate, and p-dimethylaminobenzoate. Amyl ester, N, N-dimethylbenzylamine, 4,4'-bis (diethylamino) benzophenone and the like.

[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, and adipic acid diacetate. Ethyl ester, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, 1,4-butanediol diacetate, glycerol triacetate Esters, etc.

The boiling point of the solvent is preferably 180 ° C or higher from the viewpoint of continuous ejection stability of the inkjet ink. In addition, when forming the pixel portion, the solvent needs to be removed from the ink composition before the ink composition is hardened. Therefore, from the viewpoint of easy removal of the solvent, the boiling point of the solvent is preferably 300 ° C. or lower.

In the case of using a thermosetting resin without using a photopolymerizable compound, from the viewpoint of making the ink composition uniform, and improving the fluidity of the ink composition, it is possible to form a color with less unevenness. From the viewpoint of the pixel portion (light conversion layer) of the filter, a solvent is preferably used. On the other hand, when a photopolymerizable compound is used, the light-scattering particles and the luminescent nanocrystalline particles can be dispersed in the photopolymerizable compound without a solvent. In this case, there is an advantage that the step of removing the solvent by drying is not necessary when forming the pixel portion.

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

When the ink composition is used in a photolithography method, first, when the ink composition is coated on a substrate and the ink composition contains a solvent, the ink composition is further dried to form a coating film. The coating film thus obtained is soluble to an alkaline developer, and is patterned by processing with an alkaline developer. At this time, from the viewpoint of the ease of processing the waste liquid of the developing solution, the alkaline developing solution occupies most of the cases in the case of an aqueous solution. Therefore, 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 nanocrystalline particles (quantum dots, etc.), the luminescent nanocrystalline particles are unstable to water, and the luminosity (e.g., fluorescence) is impaired by moisture. . Therefore, in this embodiment, an inkjet method is preferred, which does not require treatment with an alkaline developer (aqueous solution).

In addition, even when the coating film of the ink composition is not treated with an alkaline developer, and when the ink composition is alkali-soluble, the coating film of the ink composition easily absorbs moisture in the atmosphere. As time passes, the luminescence (e.g., fluorescence) of the luminous nanocrystalline particles (quantum dots, etc.) is gradually deteriorated. From this viewpoint, in this embodiment, the coating film of the ink composition is preferably alkali-insoluble. That is, the ink composition of this 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. The so-called coating composition of the ink composition is alkali-insoluble, which means that the solubility of the coating film of the ink composition at 25 ° C with respect to the 1% by mass potassium hydroxide aqueous solution is based on the total mass of the coating film of the ink composition It is 30% by mass or less. The dissolving amount of the coating film of the ink composition is preferably 10% by mass or less, and more preferably 3% by mass or less. In addition, the ink composition is an ink composition capable of forming an alkali-insoluble coating film. After the ink composition is coated on a substrate, the solvent composition is measured at 80 ° C for 3 minutes. The above-mentioned dissolved amount of the coating film having a thickness of 1 μm obtained by drying was confirmed.

<Manufacturing Method of Ink Composition>

Next, the manufacturing method of the ink composition of the said embodiment is demonstrated. The ink composition can be obtained, for example, by mixing the constituent components of the ink composition and performing a dispersion treatment. Hereinafter, as an example of a method for producing an ink composition, a method for producing an ink composition further containing a polymer dispersant will be described.

The method for producing an 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 applying a dispersion of light-scattering particles and light-emitting nanocrystalline particles. Step 2 of mixing. 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, a photopolymerizable compound and / or a thermosetting resin may be further mixed. By this method, the light-scattering particles can be sufficiently dispersed. Therefore, light leakage in the pixel portion can be reduced, and an ink composition excellent in ejection stability can be easily obtained.

In the step of preparing a dispersion of the light-scattering particles, a light-scattering particle, a polymer dispersant, and optionally a photopolymerizable compound, and / or a thermosetting resin may be mixed and dispersed. To prepare a dispersion of light-scattering particles. Mixing and dispersion processing can be performed using a dispersing device such as a bead mill, a paint conditioner, and a planetary mixer. 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, a bead mill or a paint conditioner is preferably used.

The method for producing an ink composition may further include a step of preparing a dispersion of the light-emitting nanocrystalline particles containing the light-emitting nanocrystalline particles and the photopolymerizable compound and / or the thermosetting resin before the second step. In this case, in the second step, a dispersion of the light-scattering particles and a dispersion of the luminescent nanocrystalline particles are mixed. By this method, the light-emitting nanocrystalline particles can be sufficiently dispersed. Therefore, light leakage in the pixel portion can be reduced, and an ink composition excellent in ejection stability can be easily obtained. In the step of preparing the dispersion of the light-emitting nanocrystalline particles, the light-emitting nanocrystal particles, the photopolymerizable compound, and / or the heat curing can be performed using the same dispersing device as the step of preparing the dispersion of the light-scattering particles. Mixing and dispersing of resin.

When the ink composition of this embodiment is used as the ink composition for the inkjet method, it is preferably applied to an inkjet recording device of a piezoelectric inkjet method using a mechanical ejection mechanism using a piezoelectric element. In the piezoelectric inkjet method, there is no case where the ink composition is instantaneously exposed to high temperature during ejection, and deterioration of luminous nanocrystalline particles is unlikely to occur, and the color filter pixel portion (light conversion layer) is also easier to obtain. As expected luminous characteristics.

<Light Conversion Layer and Color Filter>

Next, the details of the light conversion layer and the color filter using the ink composition of the above embodiment will be described with reference to the drawings. In the following description, the same or equivalent elements are designated by the same reference numerals, and repeated descriptions are omitted.

FIG. 1 is a schematic cross-sectional view of a color filter according to an 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 portions 10 and a light shielding portion 20.

The light conversion layer 30 includes, as the pixel portion 10, a first pixel portion 10 a, a second pixel portion 10 b, and a third pixel portion 10 c. The first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c are arranged in a lattice pattern so as to be sequentially repeated. The light shielding portion 20 is provided between adjacent pixel portions, that is, between the first pixel portion 10a and the second pixel portion 10b, between the second pixel portion 10b and the third pixel portion 10c, and the third pixel portion 10c. And the first pixel portion 10a. In other words, the adjacent pixel portions are separated from each other by the light shielding portion 20.

Each of the first pixel portion 10a and the second pixel portion 10b contains a cured product of the ink composition of the above embodiment. The hardened | cured material contains the luminous nanocrystal particle, a light-scattering particle, and a hardening component. The curing component is a cured product of a photopolymerizable compound and / or a thermosetting resin, and is specifically a cured product obtained by polymerizing a photopolymerizable compound and / or crosslinking a thermosetting resin. That is, the first pixel portion 10a includes the first hardened component 13a, and the first light-emitting nanocrystalline particles 11a and the first light-scattering particles 12a dispersed in the first hardened component 13a, respectively. Similarly, the second pixel portion 10b includes a second hardened component 13b, and second light-emitting nanocrystalline particles 11b and second light-scattering particles 12b dispersed in the second hardened component 13b, respectively. In the first pixel portion 10a and the second pixel portion 10b, the first hardened component 13a and the second hardened component 13b may be the same or different, and the first light-scattering particles 12a and the second light-scattering particles 12b may be the same or different. different.

The first luminescent nanocrystalline particles 11a are red luminescent nanocrystalline particles that absorb light having a wavelength in a range of 420 to 480 nm and emit light having a luminescent peak wavelength in a range of 605 to 665 nm. In other words, the first pixel portion 10a may be a red pixel portion for converting blue light into red light. The second luminescent nanocrystalline particles 11b are green luminescent nanocrystalline particles that absorb light having a wavelength in a range of 420 to 480 nm and emit light having a light emitting peak wavelength in a range of 500 to 560 nm. In other words, the second pixel portion 10b may be a green pixel portion for converting blue light into green light.

The content of the light-emitting nanocrystalline particles in the pixel portion of the hardened material containing the ink composition may be 5% by mass based on the total mass of the hardened material of the ink composition from the viewpoint that the light leakage reduction effect is more excellent. The above may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more. From the viewpoint of excellent reliability of the pixel portion, the content of the light-emitting nanocrystalline particles may be 70% by mass or less, or 60% by mass or less based on the total mass of the hardened material of the ink composition. It is 55% by mass or less, and may be 50% by mass or less.

The content of the light-scattering particles in the pixel portion of the hardened material containing the ink composition may be 0.1% by mass or more based on the total mass of the hardened material of the ink composition from the viewpoint that the light leakage reduction effect is more excellent. It may be 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, or 12% by mass or more. The content of the light-scattering particles may be 60% by mass or less based on the total mass of the hardened material of the ink composition from the viewpoint that the effect of reducing light leakage is more excellent and the viewpoint that the reliability of the pixel portion is excellent. 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, or 15% by mass or less.

The third pixel portion 10c has a transmittance of 30% or more for light having a wavelength in a range of 420 to 480 nm. Therefore, when the third pixel portion 10c uses a light source that emits light having a wavelength in a range of 420 to 480 nm, it functions as a blue pixel portion. The third pixel portion 10 c includes, for example, a cured product of the composition containing the photopolymerizable compound and / or a thermosetting resin. The hardened | cured material contains the 3rd hardening component 13c. The 3rd hardening component 13c is a hardened | cured material of a photopolymerizable compound and / or a thermosetting resin, Specifically, it is a hardened | cured material obtained by superposing | polymerizing a photopolymerizable compound and / or crosslinking a thermosetting resin. That is, the third pixel portion 10c contains a third hardened component 13c. When the third pixel portion 10c contains the hardened material, the composition containing a photopolymerizable compound and / or a thermosetting resin need only have a transmittance of 30% or more for light having a wavelength in a range of 420 to 480 nm. It may further contain components other than the photopolymerizable compound and the thermosetting resin among the components contained in the ink composition. The transmittance of the third pixel portion 10c can be measured by a micro-spectroscopy device.

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, 1 μm or more, 2 μm or more, or 3 μm or more. 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.

The light-shielding portion 20 is a so-called black matrix provided for the purpose of preventing color mixing by separating adjacent pixel portions and for preventing light leakage from a light source. The material constituting the light-shielding portion 20 is not particularly limited. Except for metals such as chromium, it can be used for hardened products of resin compositions containing light-shielding particles such as carbon particles, metal oxides, inorganic pigments, and organic pigments in the binder polymer. . As the binder polymer used herein, one or two or more kinds of polyimide resin, acrylic resin, epoxy resin, polypropylene amide, polyvinyl alcohol, gelatin, casein, cellulose, and the like can be used. Resin mixed products, photosensitive resins, O / W emulsion type resin compositions (for example, those obtained by emulsifying reactive polysiloxane), and the like. The thickness of the light shielding portion 20 may be, for example, 0.5 μm or more, and may be 10 μm or less.

The substrate 40 is a transparent substrate having light transmissivity. For example, transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plates, transparent flexible substrates such as transparent resin films, and optical resin films can be used. Wait. Among these, it is preferable to use a glass substrate made of an alkali-free glass containing no alkali component in the glass. Specifically, it is suitable for "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" manufactured by Corning, "AN100" manufactured by Asahi Glass, "OA-10G" manufactured by Nippon Electric Glass, and "OA-11". These materials have a small thermal expansion coefficient, and have excellent dimensional stability and workability during high-temperature heat treatment.

The color filter 100 having the above-mentioned light conversion layer 30 can be suitably used in a case where a light source that emits light having a wavelength in a range of 420 to 480 nm is used.

The color filter 100 can be manufactured, for example, by forming the light-shielding portion 20 on the substrate 40 in a pattern and then selectively forming the ink composition (ink-jet ink) of the above-mentioned embodiment by an inkjet method. The pixel portion forming area which is attached to the base material 40 and is divided by the light shielding portion 20 is hardened by irradiation or heating with active energy rays.

The method of forming the light-shielding portion 20 includes forming a metal thin film such as chromium on a region of one side of the base material 40 that is a boundary between a plurality of pixel portions, or a thin film of a resin composition containing light-shielding particles, and Methods for patterning thin films. 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. Examples of the method for patterning include photolithography.

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

When the ink composition is hardened 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 can be used. The wavelength of the irradiated light may be, for example, 200 nm or more and 440 nm or less. The exposure amount may be, for example, 10 mJ / cm ² or more, and may be 4000 mJ / cm ² or less.

When the ink composition is hardened 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, 10 minutes or more and 120 minutes or less.

As mentioned above, although the color filter and the light conversion layer, and one embodiment of the manufacturing method were demonstrated, this invention is not limited to the said embodiment.

For example, the light conversion layer may further include a pixel portion (blue pixel portion) including a hardened body of an ink composition containing blue luminescent nanocrystalline particles instead of or in addition to the third pixel portion 10c. In addition, a pixel portion (blue pixel portion) including a cured product of an ink composition containing blue luminescent nanocrystalline particles is provided. In addition, the light conversion layer may include a pixel portion (for example, a yellow pixel portion) including a cured product of an ink composition containing nanocrystalline particles that emit light of colors other than red, green, and blue. In these cases, it is preferable that each of the luminescent nanocrystalline particles included in each pixel portion of the light conversion layer has a maximum absorption wavelength in the same wavelength region.

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

In addition, the color filter may include an ink repellent layer composed of an ink repellent material having a width narrower than that of the light repellent portion on the pattern of the light shield. In addition, instead of providing an ink-repellent layer, a photocatalyst-containing layer as a wettable variable layer may be formed in a fully coated manner in an area including a pixel portion formation area, and then exposed to light from the photocatalyst-containing layer through a photomask. On the other hand, the ink affinity of the formation area of the pixel portion is selectively increased. Examples of the photocatalyst include titanium oxide.

The color filter may include an ink receiving layer containing hydroxypropyl cellulose or the like between the substrate and the pixel portion.

The color filter may include a protective layer on the pixel portion. This protective layer is provided in order to flatten the color filter and prevent the components contained in the pixel portion, or the components contained in the pixel portion and the components contained in the photocatalyst-containing layer from dissolving into the liquid crystal layer. As the material constituting the protective layer, those known as protective layers for color filters can be used.

In the manufacture of color filters and light conversion layers, the pixel portion may be formed by a light lithography method instead of an inkjet method. In this case, first, the ink composition is applied to the substrate in a layered manner to form an ink composition layer. Then, after exposing the ink composition layer in a pattern, development is performed using a developing solution. Thus, a pixel portion made of a hardened material of the ink composition is formed. Since the developing solution is generally alkaline, an alkali-soluble polymer is used as the binder polymer. However, from the standpoint of material use efficiency, the inkjet method is superior to the photolithography method. The reason is that in the light lithography method, in principle, about 2/3 of the material is removed, and the material becomes waste. Therefore, in this embodiment, it is preferable to use inkjet ink to form the pixel portion by an inkjet method.

In addition, the pixel portion of the light conversion layer of this embodiment may further contain a pigment having a color substantially the same as the luminescent color of the luminescent nanocrystalline particles in addition to the above-mentioned luminescent nanocrystalline particles. For example, when a pixel portion containing light-emitting nanocrystalline particles that absorb blue light and emit light is used as the pixel portion of a liquid crystal display element, blue light or quasi-white light having a peak at 450 nm is used as the light from the light source. When the concentration of the light-emitting nanocrystalline particles in the pixel portion is insufficient, 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 is mixed with light emitted from the luminescent nanocrystalline particles. From the viewpoint of preventing the color reproducibility from being reduced due to the occurrence of such color mixing, a pixel may be contained in the pixel portion of the light conversion layer. In order to make a pixel part contain a pigment, you may contain a pigment in an ink composition.

In addition, one or two of the red pixel portion (R), the green pixel portion (G), and the blue pixel portion (B) in the light conversion layer of this embodiment can be made free of a luminous nanocrystal. The pixel portion containing the color material as particles. As the color material that can be used here, a known color material can be used, and examples of the color material used for the red pixel portion (R) include a pyrrolopyrrole dione pigment and / or an anionic red organic dye. Examples of the color material used for the green pixel portion (G) are selected from the group consisting of a mixture of a halogenated copper phthalocyanine pigment, a phthalocyanine green dye, a phthalocyanine blue dye, and an azo yellow organic dye. At least one. Examples of the color material used for the blue pixel portion (B) include an ε-type copper phthalocyanine pigment and / or a cationic blue organic dye. When the use amount of these color materials is contained in the light conversion layer, it is preferable that the total mass of the pixel portion (hardened material of the ink composition) is used as a reference from the viewpoint of preventing a decrease in transmittance. It is 1 to 5 mass%.

[Example]

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.

In the examples and comparative examples, the following materials were used.

[Luminescent nanocrystalline particles]

‧QD Dispersion 1: 776785

(Product number manufactured by SIGMA-ALDRICH company, composition of QD: InP / ZnS, emission peak wavelength λem of QD: 650nm, QD content: 5mg / mL, toluene solution)

‧QD Dispersion 2: 776750

(Product number manufactured by SIGMA-ALDRICH, QD composition: InP / ZnS, QD emission peak wavelength λem: 530nm, QD content: 5mg / mL, toluene solution)

[Light scattering particles]

‧Titanium oxide 1: JR-806 (trade name manufactured by Tayca Co., Ltd., average particle diameter (volume average diameter): 300 nm)

‧Titanium oxide 2: TTO-80 (trade name manufactured by Ishihara Industry Co., Ltd., average particle diameter (volume average diameter): 60 nm)

[Photopolymerizable compound]

‧ Alicyclic epoxy monomer: Celloxide 2000 (trade name manufactured by Daicel Co., Ltd., "Celloxide" is a registered trademark)

‧Oxetane monomer: ARONE OXETANE OXT-212 (trade name manufactured by Toa Synthesis Co., Ltd., "ARONE OXETANE" is a registered trademark)

[Polymer dispersant]

‧Polymer dispersant: DISPERBYK-2155 (trade name manufactured by BYK, "DISPERBYK" is a registered trademark)

[Polymerization initiator]

‧Photocationic polymerization initiator: CPI-100P (trade name manufactured by San-Apro Co., Ltd., "CPI" is a registered trademark)

<Preparation of QD / alicyclic epoxy monomer dispersion>

(Preparation Example 1)

After mixing 400 mL of QD dispersion liquid 1 and 8 g of alicyclic epoxy monomer, toluene was removed from the QD dispersion liquid by an evaporator, thereby obtaining QD / alicyclic epoxy monomer dispersion 1 (QD Content: 20% by mass).

(Preparation Example 2)

A QD / alicyclic epoxy monomer dispersion 2 (QD content: 20% by mass) was obtained in the same manner as in Production Example 1 except that QD dispersion liquid 2 was used instead of QD dispersion liquid 1.

<Preparation of Light Scattering Particle Dispersion>

(Preparation Example 3)

1.29 g of titanium oxide, 0.13 g of a polymer dispersant, and 1.81 g of an oxetane monomer were blended. After adding the zirconia beads (diameter: 5 mm) to the obtained blend, the coating blender was shaken for 2 hours to perform dispersion treatment of the blend. Thereby, a light-scattering particle dispersion 1 is obtained.

(Preparation Example 4)

A light-scattering particle dispersion 2 was obtained in the same manner as in Production Example 3, except that titanium oxide 2 was used instead of titanium oxide 1.

(Preparation Example 5)

A light-scattering particle dispersion was obtained in the same manner as in Production Example 3 except that the blend was dispersed by using a planetary mixer (manufactured by Thinky, trade name "ARE-310") at 2000 rpm for 5 minutes. Body 3.

(Preparation Example 6)

A light-scattering particle dispersion was obtained in the same manner as in Production Example 4 except that the dispersion treatment of the blend was performed by stirring at 2000 rpm for 5 minutes using a planetary mixer (manufactured by Thinky, trade name "ARE-310"). Body 4.

(Preparation Example 7)

1.31 g of titanium oxide 1 and 1.83 g of oxetane monomer were blended. After adding the zirconia beads (diameter: 5 mm) to the obtained blend, the coating blender was shaken for 2 hours to perform dispersion treatment of the blend. Thereby, a light-scattering particle dispersion 5 is obtained.

(Preparation Example 8)

A light-scattering particle dispersion 6 was obtained in the same manner as in Production Example 7 except that titanium oxide 2 was used instead of titanium oxide 1.

(Example 1)

(1) Preparation of ink composition (inkjet ink)

After mixing 6.47 g of QD / alicyclic epoxy monomer dispersion 1, 3.23 g of light scattering particle dispersion 1, and 0.3 g of photocationic polymerization initiator, a filter with a pore size of 5 μm was used. The mixture was filtered to obtain an ink composition. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 0.35 μm. In this example, the average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition is a dynamic light-scattering Nanotrac particle size distribution meter (manufactured by Nikkiso Co., Ltd., trade name). "Nanotrac").

(2) Production of light conversion filters

The ink composition obtained in the above (1) was applied on a glass substrate (glass slide) so that the film thickness after drying became 5 μm by a spin coater. After the obtained film was dried, the dried film was irradiated with ultraviolet rays at an exposure amount of 2000 mJ / cm ² . Thereby, the ink composition is hardened, and a layer (light conversion layer) made of a cured product of the ink composition is formed on the glass substrate. A light conversion filter is obtained by the above operations.

(3) Evaluation

Using the ink composition obtained in the above (1) and the light conversion filter obtained in the above (2), light leakage evaluation and discharge stability evaluation were performed in the following order. The results are shown in Table 1.

[Light leakage evaluation]

As the surface emitting light source, a blue LED (peak emission wavelength: 450 nm) manufactured by CCS Co., Ltd. was used. A light conversion filter is set on the light source with the glass substrate side as the lower side. The integrating sphere was connected to a radiation spectrophotometer (trade name "MCPD-9800") manufactured by Otsuka Electronics Co., Ltd., and the integrating sphere was brought close to a light conversion filter provided on a blue LED. In this state, the blue LED was turned on, and the peak intensity (S) of the observed light with a wavelength of 450 nm was measured. Next, a glass substrate (glass slide) used in the production of the light conversion filter was placed on the light source instead of the light conversion filter. Except that, the light with a wavelength of 450 nm was observed in the same manner as the above method, and the measurement was performed. Peak Light Intensity (R). The light leakage rate T (peak intensity ratio: S / R × 100) of light having a wavelength of 450 nm was calculated and evaluated according to the following criteria. The smaller the light leakage rate is, the higher the color purity is.

A: T <20%

B: 20 ≦ T ≦ 50%

C: T> 50%

[Ejection Stability Evaluation]

Using an inkjet printer (manufactured by Fuji Film Dimatix, trade name "DMP-2831"), the ink composition was continuously ejected for 10 minutes. Furthermore, 16 nozzles are formed on the ink ejection head of the inkjet printer, and the amount of the ink composition ejected once per nozzle is set to 10 pL. The ejection stability was evaluated according to the following criteria.

A: Continuous ejection (continuous ejection of more than 10 nozzles out of 16 nozzles)

B: Continuous ejection is not possible (out of 16 nozzles, the number of nozzles that can be ejected continuously is 9 or less)

C: Unable to eject

(Example 2)

An ink composition was obtained in the same manner as in Example 1, except that the light-scattering particle dispersion 2 was used instead of the light-scattering particle dispersion 1. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 0.52 μm. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)

An ink composition was obtained in the same manner as in Example 1 except that QD / alicyclic epoxy monomer dispersion 2 was used instead of QD / alicyclic epoxy monomer dispersion 1. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 0.35 μm. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 4)

An ink composition was obtained in the same manner as in Example 1 except that the light-scattering particle dispersion 3 was used instead of the light-scattering particle dispersion 1. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 1.49 μm. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)

An ink composition was obtained in the same manner as in Example 1 except that the light-scattering particle dispersion 4 was used instead of the light-scattering particle dispersion 1. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 1.51 μm. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)

Use 6.55g of QD / alicyclic epoxy monomer dispersion 1, use 3.14g of light-scattering particle dispersion 5 instead of light-scattering particle dispersion 1, and use 0.31g of photocationic polymerization initiator, except Other than that, an ink composition was obtained in the same manner as in Example 1. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 1.46 μm. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)

An ink composition was obtained in the same manner as in Example 6 except that the light-scattering particle dispersion 6 was used instead of the light-scattering particle dispersion 5. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 1.32 μm. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative example 1)

After mixing 7.54 g of QD / alicyclic epoxy monomer dispersion, 2.11 g of oxetane monomer, and 0.35 g of photocationic polymerization initiator, a filter with a pore size of 5 μm was used. The mixture was filtered to obtain an ink composition. A light conversion filter was obtained in the same manner as in Example 1 except that the ink composition was used. Using the obtained ink composition and light conversion filter, light leakage evaluation and discharge stability evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

As shown in Table 1, when the ink composition of Comparative Example 1 which does not use light-scattering particles was used, significant light leakage was confirmed. In addition, as shown in Table 1, in the ink compositions of Examples 1 and 2 using the polymer dispersant and dispersing the light-scattering particles with a paint conditioner and having a particle diameter of less than 1.0 μm, the ink composition using the polymer dispersant but The ink compositions of Examples 4 and 5 which were dispersed using a planetary agitator and had a particle size greater than 1.0 μm, and Examples 6 and 5 having a particle diameter of greater than 1.0 μm without using a polymer dispersant and having a polymer dispersant dispersed by a paint conditioner Compared with the ink composition of 7, it was confirmed that excellent ejection stability can be obtained.

(Example 8)

First, a substrate (BM substrate) having a light-shielding portion called a black matrix (BM) was produced in the following procedure. That is, a black resist ("CFPR BK" manufactured by Tokyo Yingka Kogyo Co., Ltd.) is applied to a glass substrate ("OQ-10G" manufactured by Nippon Electric Glass Co., Ltd.) made of an alkali-free glass, followed by pattern exposure. , Development and baking, thereby forming a patterned light-shielding portion. 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 is a pattern having an opening portion of a sub-pixel corresponding to 200 μm × 600 μm, the line width is 20 μm, and the thickness is 2.6 μm.

Then, the ink composition obtained in Example 1 was printed on the opening portion of the BM substrate by an inkjet method, and then irradiated with ultraviolet rays. Then, it heated at 150 degreeC for 30 minutes in nitrogen atmosphere. Thereby, the ink composition is hardened to form a pixel portion composed of a hardened material of the ink composition. The obtained pixel portion is a pixel portion that converts blue light into red light. The thickness of the pixel portion is 2.1 μm. Through the above operations, a patterned light conversion filter is obtained.

(Example 9)

A BM substrate was prepared in the same manner as in Example 8. Next, the ink composition obtained in Example 1 and the ink composition obtained in Example 3 were printed by an inkjet method on an opening portion on a BM substrate, and then the ink composition was cured by irradiating ultraviolet rays. Thereby, a pixel portion that converts red light into blue light and a pixel portion that converts blue light into green light are formed on the BM substrate. Through the above operations, a patterned light conversion filter having a plurality of pixel portions is obtained.

Claims (22)

    An ink composition containing light-emitting nanocrystalline particles, light-scattering particles, a photopolymerizable compound, and / or a thermosetting resin.         For example, the ink composition according to the first patent application scope further contains a polymer dispersant.         For example, the ink composition according to item 2 of the patent application range, wherein the weight average molecular weight of the polymer dispersant is 1,000 or more.         For example, the ink composition according to any one of claims 1 to 3 of the patent application scope, which contains the above-mentioned photopolymerizable compound.         For example, the ink composition according to item 4 of the application, wherein the photopolymerizable compound is a photoradical polymerizable compound.         For example, the ink composition according to item 4 of the application, wherein the photopolymerizable compound is a photocationic polymerizable compound.         For example, the ink composition according to claim 4 of the application, wherein the photopolymerizable compound is alkali-insoluble.         The ink composition according to any one of claims 1 to 3 of the patent application scope, which contains the above-mentioned thermosetting resin.         For example, the ink composition according to item 8 of the application, wherein the thermosetting resin is alkali-insoluble.         For example, the ink composition according to any one of claims 1 to 3 can form an alkali-insoluble coating film.         For example, the ink composition according to any one of claims 1 to 3, wherein the average particle diameter of the light-scattering particles is 0.05 to 1.0 μm.         For example, the ink composition according to any one of claims 1 to 3, wherein the average particle diameter of the light-scattering particles is 0.3 to 0.6 m.         The ink composition according to any one of claims 1 to 3, wherein the light-scattering particles contain a material selected from the group consisting of titanium oxide, aluminum oxide, zirconia, zinc oxide, calcium carbonate, barium sulfate, and silicon dioxide. At least one member of the group.         For example, the ink composition of any one of claims 1 to 3 has a surface tension of 20 to 40 mN / m.         For example, the ink composition of any one of claims 1 to 3 has a viscosity of 2 to 20 mPa‧s.         For example, the ink composition according to any one of claims 1 to 3 in the patent application scope further contains a solvent having a boiling point of 180 ° C or higher.         For example, the ink composition according to any one of claims 1 to 3 is applied to a color filter.         For example, the ink composition according to any one of claims 1 to 3 is applied by an inkjet method.         A light conversion layer includes a plurality of pixel portions, and the plurality of pixel portions include: a pixel portion containing a hardened body of the ink composition according to any one of claims 1 to 18 of a patent application.         For example, the light conversion layer according to item 19 of the patent application scope further includes a light shielding portion provided between the plurality of pixel portions, and the plurality of pixel portions include: a first pixel portion containing the hardened material and containing an absorption 420 Light-emitting nanocrystalline particles emitting light with a wavelength in the range of ~ 480nm and light having a peak wavelength of emission in the range of 605-665nm are used as the above-mentioned light-emitting nanocrystalline particles; and a second pixel portion containing the hardened material, The light-emitting nanocrystalline particles include light-emitting nanocrystalline particles that absorb light having a wavelength in a range of 420 to 480 nm and emit light having a light-emitting peak wavelength in a range of 500 to 560 nm.         For example, the light conversion layer in the scope of application for the patent No. 20, wherein the plurality of pixel portions further includes a third pixel portion, and its transmittance for light having a wavelength in a range of 420 to 480 nm is 30% or more.         A color filter includes a light conversion layer according to any one of claims 19 to 21.