KR102466272B1 - Ink composition, light conversion layer, and color filter - Google Patents

Abstract

The present invention provides an ink composition containing luminescent nanocrystal particles having a core/shell structure, light-scattering particles, a photopolymerizable compound, and/or a thermosetting resin.

Description

Ink composition, light conversion layer and color filter {INK COMPOSITION, LIGHT CONVERSION LAYER, AND COLOR FILTER}

The present 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 curable resist material containing, for example, red organic pigment particles or green organic pigment particles, an alkali-soluble resin and/or an acrylic monomer, and It has been manufactured by a lithography method.

In recent years, there has been a strong demand for low power consumption of displays, and instead of the above-mentioned red organic pigment particles or green organic pigment particles, for example, quantum dots, quantum rods, and other inorganic phosphor particles, etc. luminescent nanocrystal particles are used, and red pixels are used. , A method of forming a color filter pixel portion such as a green pixel has been actively researched.

[0005] However, in the method for manufacturing a color filter using the photolithography method, there is a drawback in that resist materials other than the pixel portion containing relatively expensive luminescent nanocrystal particles are wasted due to the characteristics of the manufacturing method. Under these circumstances, in order to eliminate the waste of the resist material as described above, the formation of the photoconversion substrate pixel portion by the inkjet method has begun to be examined (Patent Document 1).

International Publication No. 2008／001693

When a color filter pixel portion (hereinafter, simply referred to as “pixel portion”) is formed of an ink composition using luminescent nanocrystal particles, there is a case where light from a light source leaks from the pixel portion without being absorbed by the luminescent nanocrystal particles. have. Since such leakage light deteriorates the color reproducibility of the pixel portion, it is necessary to reduce it as much as possible.

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

One aspect of the present invention relates to an ink composition containing luminescent nanocrystal particles, light scattering particles, a photopolymerizable compound, and/or a thermosetting resin. According to this ink composition, leakage light in a pixel part can be reduced.

The ink composition may further contain a polymer dispersant. 1000 or more may be sufficient as the weight average molecular weight of this polymeric dispersing agent.

When the ink composition contains a photopolymerizable compound, the photopolymerizable compound may be a photoradically polymerizable compound or a photocationically polymerizable compound. In addition, 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, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silica.

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

The ink composition may have a viscosity of 2 to 20 mPa·s.

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

The ink composition may be for color filters.

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

One aspect of the present invention, as a light conversion layer having a plurality of pixel units, relates to a light conversion layer having a plurality of pixel units including a cured product of the ink composition described above. According to this light conversion layer, leakage light in a pixel part can be reduced.

The light conversion layer may further include a light blocking portion provided between the plurality of pixel portions, and the plurality of pixel portions include the cured product, and absorb light having a wavelength in the range of 420 to 480 nm as luminescent nanocrystal particles. A first pixel portion containing luminescent nanocrystal particles emitting light having a luminescence peak wavelength in the range of 605 to 665 nm, and the cured product, and further comprising luminescent nanocrystal particles having a wavelength in the range of 420 to 480 nm You may have a second pixel portion containing luminescent nanocrystal particles that absorb light and emit light having a luminescence peak wavelength in the range of 500 to 560 nm.

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

One aspect of the present invention relates to a color filter having the light conversion layer described above. According to this color filter, leakage light in a pixel part can be reduced.

ADVANTAGE OF THE INVENTION According to this invention, the ink composition which can reduce leakage light, and the light conversion layer and color filter using this ink composition can be provided.

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

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<Ink composition>

The ink composition of one embodiment contains luminescent nanocrystal particles, light scattering particles, a photopolymerizable compound, and/or a thermosetting resin. An ink composition of one embodiment is an ink composition for color filters used to form a pixel portion of a color filter by a method such as a photolithography method or an inkjet method, for example.

The ink composition of one embodiment is suitably used for the use of forming a color filter pixel part by an inkjet method. In the case of forming a color filter pixel portion by an inkjet method using a conventional ink composition, it is difficult to reduce leakage light from the pixel portion. On the other hand, according to the ink composition of the embodiment, even if it is an inkjet method, it is possible to obtain a pixel portion excellent in the leakage light reduction effect.

Hereinafter, an ink composition for color filters (inkjet ink for color filters) used in an inkjet method will be described as an example.

[Luminescent nanocrystal particles]

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

The luminescent nanocrystal particles can emit light (fluorescence or phosphorescence) of a different wavelength from the absorbed wavelength, for example, by absorbing light of a predetermined wavelength. The luminescent nanocrystal particles may be red luminescent nanocrystal particles that emit light (red light) having a peak emission wavelength in the range of 605 to 665 nm, or emit light (green light) having a peak emission wavelength in the range of 500 to 560 nm. It may be a green luminescent nanocrystal particle that emits, or may be a blue luminescent nanocrystal particle that emits 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 these luminescent nanocrystal particles. In addition, the light absorbed by the luminescent nanocrystal particles may be, for example, light with a wavelength in the range of 400 nm or more and less than 500 nm (blue light) or light with a wavelength in the range of 200 nm to 400 nm (ultraviolet light). . In addition, the emission peak wavelength of the luminescent nanocrystal particles can be confirmed in a fluorescence spectrum or phosphorescence spectrum measured using, for example, an ultraviolet and visible spectrophotometer.

The red luminescent nanocrystal particles are 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less, 643 nm or less Below, 640 nm or less, 637 nm or less, 635 nm or less, 632 nm or less, or 630 nm or less is preferable, and 628 nm or more, 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more , it is preferable to have an emission peak wavelength at 610 nm or more, 607 nm or more, or 605 nm or more. These upper limit values and lower limit values can be combined arbitrarily. In addition, also in the following similar description, the upper limit value and the lower limit value described individually can be combined arbitrarily.

The green light-emitting nanocrystal particles are 560 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less, 532 nm or less. It is preferable to have an emission peak wavelength of 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. Alternatively, it is preferable to have an emission peak wavelength of 500 nm or more.

Blue luminescent nanocrystal particles are 480 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less, 452 nm It is preferable to have an emission peak wavelength of 450 nm or less, 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. It is preferable to have an emission peak wavelength at .

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

The luminescent nanocrystal particle may be a luminescent nanocrystal particle (luminescent semiconductor nanocrystal particle) containing a semiconductor material. Examples of the luminescent semiconductor nanocrystal particles include quantum dots (hereinafter also referred to as "QDs"), quantum rods, and the like. Among these, quantum dots are preferable from the viewpoint of easy control of the emission spectrum, reliability, reduction in production cost, and improvement in mass productivity.

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

The luminescent nanocrystal particles are at least selected from the group consisting of group II-VI semiconductors, group III-V semiconductors, group I-III-VI semiconductors, group IV semiconductors, and group I-II-IV-VI semiconductors as a semiconductor material. It is preferable to include one type of 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, HgZnSeTe, HgZnSTe; GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe ₂ , CuGaSe ₂ , CuInS ₂ , CuGaS ₂ , CuInSe ₂ , AgInS ₂ , AgGaSe ₂ , AgGaS ₂ , C, Si and Ge. The luminescent semiconductor nanocrystal particles are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO from the viewpoint of easy control of the emission spectrum, securing reliability, reducing production cost, and improving mass productivity. , HgS, HgSe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaS ₂ , AgGaSe ₂ , AgGaTe ₂ , CuInS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaS ₂ , CuGaSe ₂ , CuGaTe ₂ , Si, C, Ge, and Cu ₂ ZnSnS ₄ It is preferable to include at least one selected from the group consisting of.

Examples of red light-emitting semiconductor nanocrystal particles include CdSe nanocrystal particles, CdSe rod-shaped nanocrystal particles, and rod-shaped nanocrystal particles having a core-shell structure, wherein the shell portion is CdS and the inner core portion is CdSe nanocrystal particles, rod-shaped nanocrystal particles having a core-shell structure, wherein the shell portion is CdS and the inner core portion is ZnSe, and nanocrystal particles having a core-shell structure, the shell portion Nanocrystal particles of CdS and the inner core portion being CdSe, nanocrystal particles having a core-shell structure, wherein the shell portion is CdS and the inner core portion is ZnSe, nanocrystal particles of a mixed crystal of CdSe and ZnS, CdSe Rod-like nanocrystal grains of mixed crystal with ZnS, nanocrystal grains of InP, nanocrystal grains of InP, nanocrystal grains of InP rod-like, nanocrystal grains of mixed crystal of CdSe and CdS, nanocrystal grains of mixed crystal of CdSe and CdS, rod-like nanocrystals Crystal grains, nanocrystal grains of a mixed crystal of ZnSe and CdS, rod-shaped nanocrystal grains of a mixed crystal of ZnSe and CdS, and the like are exemplified.

As the green light-emitting semiconductor nanocrystal particles, for example, CdSe nanocrystal particles, rod-shaped nanocrystal particles of CdSe, mixed crystal nanocrystal particles of CdSe and ZnS, rod-shaped nanocrystal particles of mixed crystal of CdSe and ZnS, etc. can be heard

Examples of blue light-emitting semiconductor nanocrystal particles include ZnSe nanocrystal particles, ZnSe rod-shaped nanocrystal particles, ZnS nanocrystal particles, ZnS rod-shaped nanocrystal particles, and core-shell structured nanocrystal particles. As a nanocrystal particle in which the shell portion is ZnSe and the inner core portion is ZnS, a rod-shaped nanocrystal having a core-shell structure, a nanocrystal particle in which the shell portion is ZnSe and the inner core portion is ZnS, and a nanocrystal of CdS particles, rod-shaped nanocrystal particles of CdS, and the like. Semiconductor nanocrystal particles have the same chemical composition, and the color to be emitted from the particles can be changed to either red or green by changing their average particle diameter. In addition, it is preferable to use semiconductor nanocrystal particles that, as such, have as little adverse effects on the human body or the like as possible. When semiconductor nanocrystal particles containing cadmium, selenium, etc. are used as luminescent nanocrystal particles, semiconductor nanocrystal particles that do not contain the element (cadmium, selenium, etc.) are selected and used alone, or the element is used as much as possible. It is preferable to use it in combination with other luminescent nanocrystal particles so as to reduce it.

The shape of the luminescent nanocrystal particle is not particularly limited, and may be an arbitrary geometric shape or an arbitrary irregular shape. The shape of the luminescent nanocrystal particle may be, for example, spherical, ellipsoidal, pyramidal, disk, branched, reticular, rod or the like. However, as the luminescent nanocrystal particles, it is preferable to use less directional particles (for example, spherical, tetrahedral, etc.) in terms of higher uniformity and fluidity of the ink composition.

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

The luminescent nanocrystal particle preferably has an organic ligand on its surface from the viewpoint of dispersion stability. The organic ligand may be coordinately bonded to the surface of the luminescent nanocrystal particle, for example. In other words, the surface of the luminescent nanocrystal particle may be passivated by an organic ligand. In addition, when the ink composition further contains a polymer dispersant described later, the luminescent nanocrystal particles may have a polymer dispersant on their surfaces. In this embodiment, for example, the organic ligand may be removed from the luminescent nanocrystal particle having the organic ligand described above, and the polymer dispersant may be bonded to the surface of the luminescent nanocrystal particle by exchanging the organic ligand with the polymer dispersant. However, from the viewpoint of dispersion stability when used as an inkjet ink, it is preferable that a polymer dispersant be blended with the luminescent nanocrystal particles with organic ligands still coordinated.

As an organic ligand, for example, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, hexyl phosphonic acid (HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA).

As the luminescent nanocrystal particles, those dispersed in colloidal form in organic solvents, photopolymerizable compounds, and the like can be used. The surface of the luminescent nanocrystal particles in a dispersed state in an organic solvent is preferably passivated by the organic ligand described above. Examples of the organic solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or mixtures thereof. have.

As the luminescent nanocrystal particles, commercial products can be used. Commercially available products of luminescent nanocrystal particles include, for example, indium phosphorus/zinc sulfide, D-dot, CuInS/ZnS, and InP/ZnS available from NN-Labose, and Aldorich.

The content of the luminescent nanocrystal particles may be 5% by mass or more, 10% by mass or more, or 15% by mass or more based on the mass of the non-volatile matter of the ink composition, from the viewpoint of a more excellent effect of reducing leakage light. , 20 mass % or more may be sufficient, 30 mass % or more may be sufficient, and 40 mass % or more may be sufficient. The content of the luminescent nanocrystal particles may be 70% by mass or less, may be 60% by mass or less, may be 55% by mass or less, based on the mass of the non-volatile matter of the ink composition, may be 50% by mass or less, from the viewpoint of excellent ejection stability. It may be less than %. In addition, in this specification, "the mass of the non-volatile matter of an ink composition" refers to the mass excluding the mass of the solvent from the total mass of an ink composition, when an ink composition contains a solvent, and the ink composition contains a solvent If not, 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 can scatter light from a light source irradiated to the color filter pixel unit.

Examples of the material constituting the light-scattering particles include simple metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; Silica, barium sulfate, barium carbonate, calcium carbonate, talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, metal oxides such as zinc oxide; metal carbonates such as magnesium carbonate, barium carbonate, bismuth carbonate, and calcium carbonate; metal hydroxides such as aluminum hydroxide; and complex oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate, and metal salts such as bismuth nitrate. The light-scattering particles preferably contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silica, from the viewpoint of a more excellent reduction effect of light leakage. It is more preferable to include at least 1 sort(s) selected from the group which consists of titanium, barium sulfate, and calcium carbonate.

The light-scattering particles may have a spherical shape, a filament shape, an irregular shape, or the like. However, as the light-scattering particles, it is preferable to use particles with little directionality (for example, spherical, tetrahedral, etc.) as the particle shape from the viewpoint of further enhancing the uniformity, flowability and light-scattering properties of the ink composition. do.

The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 0.05 μm or more, 0.2 μm or more, or 0.3 μm or more from the viewpoint of a more excellent light leakage reduction effect. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 1.0 µm or less, 0.6 µm or less, or 0.4 µm or less from the viewpoint of excellent ejection stability. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition is 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, and 0.3 to 1.0 µm. μm, 0.3 to 0.6 μm, or 0.3 to 0.4 μm may be sufficient. From the standpoint of obtaining such average particle diameter (volume average diameter) easily, the average particle diameter (volume average diameter) of the light-scattering particles used may be 50 nm or more and 1000 nm or less. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition is obtained by measuring with a dynamic light-scattering nanotrack particle size distribution analyzer and calculating the volume average diameter. In addition, the average particle diameter (volume average diameter) of the light-scattering particles to be used is obtained by measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope, for example, and calculating the volume average diameter.

The content of the light-scattering particles may be 0.1% by mass or more, 1% by mass or more, or 5% by mass or more based on the mass of the non-volatile content of the ink composition, from the viewpoint of a more excellent effect of reducing leakage light. 7 mass % or more may be sufficient, 10 mass % or more may be sufficient, or 12 mass % or more may be sufficient. The content of the light-scattering particles may be 60% by mass or less, may be 50% by mass or less, based on the mass of the non-volatile matter of the ink composition, from the viewpoint of a more excellent reduction effect of leaked light and excellent discharge stability, 40 It may be 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less. In this embodiment, since the ink composition contains a polymeric dispersant, the light-scattering particles can be favorably dispersed even when the content of the light-scattering particles is within the above range.

The mass ratio of the content of the light-scattering particles to the content of the luminescent nanocrystal particles (light-scattering particles/luminescent nanocrystal particles) may be 0.1 or more, may be 0.2 or more, or 0.5 or more from the viewpoint of a more excellent reduction effect of light leakage. do. The mass ratio (light scattering particles/luminescent nanocrystal particles) may be 5.0 or less, 2.0 or less, or 1.5 or less, from the viewpoint of a more excellent light leak reduction effect and excellent continuous ejection property during inkjet printing. In addition, it is thought that the light leakage reduction by light-scattering particle|grains is based on the following mechanism. That is, when no light-scattering particles exist, it is considered that the backlight light only passes almost straight through the inside of the pixel portion, and there is little chance of being absorbed by the luminescent nanocrystal particles. On the other hand, when the light-scattering particles are present in the same pixel portion as the luminescent nanocrystal particles, the backlight is scattered in all directions within the pixel portion, and the luminescent nanocrystal particles can receive light. Even if the same backlight is used, it is thought that the amount of light absorption in the pixel portion increases. As a result, it is thought that it became possible to prevent light leakage by this mechanism.

[Photopolymerizable Compound]

The photopolymerizable compound of the present embodiment is a radical photopolymerizable compound or a photocationically polymerizable compound that is polymerized by light irradiation, and may be a photopolymerizable monomer or oligomer. These are used together with a photoinitiator. The photoradical polymerizable compound is used with a photoradical polymerization initiator, and the photocationically polymerizable compound is used with a photocationic polymerization initiator. In other words, the ink composition may contain a photopolymerizable component including a photopolymerizable compound and a photopolymerization initiator, or may contain a photoradical polymerizable component including a photoradical polymerizable compound and a photoradical polymerization initiator. You may contain the photocationically polymerizable component containing an ionically polymerizable compound and a photocationic polymerization initiator. A radical photopolymerizable compound and a photocationically polymerizable compound may be used in combination, a compound having photoradical polymerization and photocationic polymerization may be used, or a photoradical polymerization initiator and a photocationic polymerization initiator may be used together. A photopolymerizable compound may be used individually by 1 type, and may use 2 or more types together.

As a radically photopolymerizable compound, a (meth)acrylate compound is mentioned. The (meth)acrylate compound may be a monofunctional (meth)acrylate having one (meth)acryloyl group or a polyfunctional (meth)acrylate having a plurality of (meth)acryloyl groups. Monofunctional (meth)acrylates and polyfunctional from the viewpoint of excellent fluidity when used as ink, better discharge stability, and a viewpoint of suppressing the decrease in smoothness due to cure shrinkage at the time of color filter production It is preferable to use a combination of (meth)acrylates. In addition, in this specification, (meth)acrylate means "acrylate" and the "methacrylate" corresponding to it. The same applies to the expression "(meth)acryloyl".

Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, and 2- Ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (metha)acrylate ) Acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclophen Tenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate Acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy) ) ethyl] tetrahydrophthalimide and the like.

The polyfunctional (meth)acrylate may be bifunctional (meth)acrylate, trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, pentafunctional (meth)acrylate, hexafunctional (meth)acrylate, or the like. and, for example, di(meth)acrylate in which two hydroxyl groups of a diol compound are substituted by (meth)acryloyloxy groups, and two or three hydroxyl groups of a triol compound are replaced by (meth)acryloyloxy groups. di- or tri(meth)acrylates substituted with may be used.

Specific examples of the bifunctional (meth)acrylate include 1,3-butylene glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,5-pentanedioldi(meth)acrylate, 3-Methyl-1,5-pentanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, 1,8-octanedioldi(meth)acrylate Acrylate, 1,9-nonanedioldi(meth)acrylate, tricyclodecanedimethanoldi(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di( meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, tris(2) -Di(meth)acrylate in which two hydroxyl groups of hydroxyethyl)isocyanurate are substituted by (meth)acryloyloxy groups, obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol Di(meth)acrylate in which two hydroxyl groups of diol are substituted by (meth)acryloyloxy groups, and two hydroxyl groups of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A are (meth) Di(meth)acrylate substituted by acryloyloxy group, two hydroxyl groups of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane are substituted by (meth)acryloyloxy group di(meth)acrylate obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, di(meth)acrylate in which two hydroxyl groups of a diol are substituted by (meth)acryloyloxy groups can be heard

Specific examples of the trifunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, glycerin triacrylate, pentaerythritol tri(meth)acrylate, and 3 moles or more of ethylene oxide or propylene oxide per mole of trimethylolpropane. Tri(meth)acrylate etc. in which three hydroxyl groups of the triol obtained by adding are substituted by the (meth)acryloyloxy group are mentioned.

As a specific example of tetrafunctional (meth)acrylate, pentaerythritol tetra (meth)acrylate is mentioned.

As a specific example of pentafunctional (meth)acrylate, dipentaerythritol penta (meth)acrylate is mentioned.

As a specific example of hexafunctional (meth)acrylate, dipentaerythritol hexa(meth)acrylate is mentioned.

The poly(meth)acrylate may be a poly(meth)acrylate in which a plurality of hydroxyl groups of dipentaerythritol, such as dipentaerythritol hexa(meth)acrylate, are substituted with (meth)acryloyloxy groups.

The (meth)acrylate compound may be an ethylene oxide-modified phosphoric acid (meth)acrylate or an ethylene oxide-modified alkyl phosphoric acid (meth)acrylate having a phosphoric acid group.

Examples of photocationically polymerizable compounds include epoxy compounds, oxetane compounds, and vinyl ether compounds.

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

It is also possible to use a commercial item as an epoxy compound. As a commercial item of an epoxy compound, "Celoxide 2000", "Celoxide 3000", "Celoxide 4000", etc. made by Daisel Chemical Industry Co., Ltd. can be used, for example.

Examples of the cationic polymerizable oxetane compound include 2-ethylhexyloxetane, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, and 3-hydroxymethyl-3-propyloxetane. , 3-hydroxymethyl-3-n-butyloxetane, 3-hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane , 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3 -Hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane, 3-hydroxybutyl-3-methyloxetane, etc. have.

It is also possible to use a commercial item as an oxetane compound. As a commercial item of an oxetane compound, it is Toagosei Co., Ltd. Aron oxetane series ("OXT-101", "OXT-212", "OXT-121", "OXT-221" etc.), for example; "Celoxide 2021", "Celoxide 2021A", "Celoxide 2021P", "Celoxide 2080", "Celoxide 2081", "Celoxide 2083", "Celoxide 2085" manufactured by Daisel Chemical Industry Co., Ltd. ”, “Epolide GT300”, “Epolide GT301”, “Epolide GT302”, “Epolide GT400”, “Epolide GT401” and “Epolide GT403”; "Cyracure UVR-6105", "Cyracure UVR-6107", "Cyracure UVR-6110", "Cyracure UVR-6128", "ERL4289" and "Cyracure UVR-6105" manufactured by Dow Chemical Nippon Co., Ltd. ERL4299” etc. can be used. In addition, a known oxetane compound (for example, the oxetane compound described in Japanese Patent Application Publication No. 2009-40830, etc.) can also be used.

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

Moreover, as a photopolymerizable compound in this embodiment, the photopolymerizable compound of Paragraph 0042 of Unexamined-Japanese-Patent No. 2013-182215 - 0049 can also be used.

In the ink composition of the present embodiment, when the curable component is composed of only a photopolymerizable compound or a photopolymerizable compound as a main component, the above photopolymerizable compound is a bifunctional or higher polyfunctional having two or more polymerizable functional groups in one molecule. Since the durability (strength, heat resistance, etc.) of hardened|cured material can be further improved, it is more preferable to use the photopolymerizable compound of <RTI ID=0.0>as an essential component.

The photopolymerizable compound may be alkali insoluble from the viewpoint of obtaining a highly reliable color filter pixel portion. In the present specification, the photopolymerizable compound is insoluble in alkali means that the amount of dissolution of the photopolymerizable compound at 25 ° C. in 1% by mass aqueous solution of potassium hydroxide is 30% by mass or less based on the total mass of the photopolymerizable compound. it means. The dissolution 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 is determined from the viewpoint of easily obtaining an appropriate viscosity as an inkjet ink, from the viewpoint of improving the curability of the ink composition, and from the viewpoint of improving the solvent resistance and wear resistance of the pixel portion (cured product of the ink composition). It may be 10 mass% or more, 15 mass% or more, or 20 mass% or more based on the mass of the non-volatile matter of the composition. The content of the photopolymerizable compound may be 90% by mass or less based on the mass of the non-volatile content of the ink composition from the viewpoint of easily obtaining an appropriate viscosity as an inkjet ink and from the viewpoint of obtaining better optical properties (light leakage) , 80 mass % or less may be sufficient, 70 mass % or less may be sufficient, 60 mass % or less may be sufficient, and 50 mass % or less may be sufficient.

The photopolymerizable compound has a crosslinkable group from the viewpoint of excellent stability of the picture portion (cured product of the ink composition) (for example, it can suppress deterioration over time and is excellent in high-temperature storage stability and moist heat storage stability). You may have it. A crosslinkable group is a functional group that reacts with another crosslinkable group by heat or active energy rays (eg, ultraviolet rays), and examples thereof include an epoxy group, an oxetane group, a vinyl group, an acryloyl group, an acryloyloxy group, and a vinyl group. An ether group etc. are mentioned.

[Photoradical polymerization initiator]

As the radical photopolymerization initiator, a molecular cleavage type or hydrogen abstraction type photo radical polymerization initiator is suitable.

Examples of the molecular cleavage type photo-radical polymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl- 2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, (2,4, 6-trimethylbenzoyl) ethoxyphenyl phosphine oxide etc. are used suitably. Other than these molecular cleavage type photo-radical polymerization initiators, 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one may be used in combination. do.

Benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenyl sulfide etc. are mentioned as a hydrogen withdrawal type photoradical polymerization initiator. A photo-radical polymerization initiator of a molecular cleavage type and a photo-radical polymerization initiator of a hydrogen withdrawal type may be used in combination.

[Photocationic polymerization initiator]

Examples of the photocationic polymerization initiator include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; polyaryliodonium salts such as diphenyliodonium hexafluoroantimonate and p-nonylphenyliodonium hexafluoroantimonate; and the like.

A commercial item can also be used as a photocationic polymerization initiator. Commercially available products include sulfonium salt-based photocationic polymerization initiators such as "CPI-100P" manufactured by San Afro, acylphosphine oxide compounds such as "Lucirin TPO" manufactured by BASF, "Irgacure 907" and "Irgacure 819" manufactured by BASF, "Irgacure 379EG", "Irgacure 184", "Irgacure PAG290", etc. are mentioned.

The content of the photopolymerization initiator may be 0.1 parts by mass or more, 0.5 parts by mass or more, or 1 part by mass or more with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of curability of the ink composition. The content of the photopolymerization initiator may be 40 parts by mass or less, 30 parts by mass or less, or even 20 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of the temporal stability of the picture element portion (cured product of the ink composition). do.

[Thermosetting resin]

In the present embodiment, the thermosetting resin is a resin that functions as a binder in a cured product and is crosslinked and cured by heat. A thermosetting resin has a curable group. Examples of the curable group include an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxy group, a methylol group, and the like, and excellent heat resistance and storage stability of the cured product of the ink composition, and a light-shielding portion (e.g., black matrix) and substrate From the viewpoint of excellent adhesion to the surface, an epoxy group is preferable. The thermosetting resin may have one type of curable group or may have two or more types of curable groups.

Further, among thermosetting resins, resins having photoradical polymerization (polymerization by irradiation of light when used with a photoradical polymerization initiator) and photocationic polymerization (when used with a photocationic polymerization initiator) resins that polymerize by irradiation of light) are included. When the ink composition contains a thermosetting resin having photo-radical polymerization and a photo-radical polymerization initiator, the thermosetting resin having photo-radical polymerization is classified as a photo-radical polymerization 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 (copolymer) of a plurality of types of monomers. In addition, any of a random copolymer, a block copolymer, and a graft copolymer may be sufficient as a thermosetting resin.

As the thermosetting resin, a compound having two or more thermosetting functional groups in one molecule is used, and is usually used in combination with a curing agent. When using a thermosetting resin, you may further add a catalyst (hardening accelerator) which can accelerate a thermosetting reaction. In other words, the ink composition may contain a thermosetting component containing a thermosetting resin (and a curing agent and curing accelerator used as needed). Moreover, in addition to these, you may further use a polymer which itself has no polymerization reactivity.

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") may be used. "Epoxy resin" includes both monomeric epoxy resins and polymeric epoxy resins. The number of epoxy groups that the polyfunctional epoxy resin has in one molecule is preferably 2 to 50, more preferably 2 to 20. The epoxy group may be a structure having an oxysilane ring structure, and may be, for example, a glycidyl group, an oxyethylene group, an epoxycyclohexyl group or the like. As the epoxy resin, known polyhydric epoxy resins that can be cured with carboxylic acid are exemplified. Such epoxy resins are widely disclosed, for example, in "Epoxy Resin Handbook", edited by Masaki Shinbo, between Daily Industrial Newspapers (1987), etc., and it is possible to use them.

Examples of the thermosetting resin having an epoxy group (including polyfunctional epoxy resins) include a polymer of a monomer having an oxysilane ring structure and a copolymer of a monomer having an oxysilane ring structure and another monomer. As specific polyfunctional epoxy resins, polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate- Glycidylmethacrylate copolymer, 2-hydroxyethylmethacrylate-glycidylmethacrylate copolymer, (3-ethyl-3-oxetanyl)methylmethacrylate-glycidylmethacrylate copolymer A polymer, styrene-glycidyl methacrylate, etc. are mentioned. Moreover, as a thermosetting resin of this embodiment, the compound of Paragraph 0044 of Unexamined-Japanese-Patent No. 2014-56248 - 0066 can also be used.

Examples of the polyfunctional epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, diphenyl ether type epoxy resins, hydroquinone type epoxy resins, Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylol Ethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A containing nucleus polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, glyoxysal type epoxy resins, alicyclic type epoxy resins, heterocyclic type epoxy resins and the like can be used.

More specifically, bisphenol A type epoxy resins such as trade name "Epicoat 828" (manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy resins such as trade name "YDF-175S" (manufactured by Toto Kasei Co., Ltd.), trade name "YDB-715 brominated bisphenol A-type epoxy resins such as " (manufactured by Toto Kasei Co., Ltd.), bisphenol S-type epoxy resins such as trade name "EPICLON EXA1514" (manufactured by DIC Corporation), trade name "YDC-1312" (manufactured by Toto Kasei Co., Ltd.), etc. Naphthalene-type epoxy resins such as hydroquinone type epoxy resins, trade names "EPICLON EXA4032", "HP-4770", "HP-4700", "HP-5000" (manufactured by DIC Corporation), trade names "Epicot YX4000H" ( Biphenyl type epoxy resins such as Japan Epoxy Resin Co., Ltd.), bisphenol A type novolak-type epoxy resins such as trade name "Epicoat 157S70" (Japan Epoxy Resin Co., Ltd.), trade name "Epicoat 154" (Japan Epoxy Resin Co., Ltd.), trade name Phenol novolak-type epoxy resins such as "YDPN-638" (manufactured by Toto Kasei Co., Ltd.), cresol novolac-type epoxy resins such as trade name "YDCN-701" (manufactured by Toto Kasei Co.), trade names "EPICLON HP-7200", " HP-7200H” (manufactured by DIC Co., Ltd.) and other dicyclopentadienephenol type epoxy resins, trade name “Epicoat 1032H60” (manufactured by Japan Epoxy Resin Co., Ltd.) and other trishydroxyphenylmethane type epoxy resins, trade name “VG3101M80” ( Trifunctional type epoxy resins such as Mitsui Chemicals Co., Ltd.), tetraphenylolethane type epoxy resins such as trade name "Epicoat 1031S" (manufactured by Japan Epoxy Resin Co., Ltd.), trade name "Denacol EX-411" (manufactured by Nagase Sei Kogyo Co., Ltd.), etc. tetrafunctional type epoxy resins, hydrogenated bisphenol A type epoxy resins such as trade name “ST-3000” (manufactured by Toto Kasei Co., Ltd.), glycidyl ester type epoxy resins such as trade name “Epicoat 190P” (manufactured by Japan Epoxy Resin Co., Ltd.), Glycidylamine type epoxy resins such as trade name "YH-434" (manufactured by Toto Kasei Co., Ltd.), glycidylamine type epoxy resins such as trade name "YDG-414" (manufactured by Toto Kasei Co., Ltd.), trade name "Epolide GT-401" 」 (manufactured by Daisel Chemical Co., Ltd.), etc., alicyclic polyfunctional epoxidation Heterocyclic epoxy resins, such as compound and triglycidyl isocyanate (TGIC), etc. can be illustrated. Moreover, if necessary, as an epoxy reactive diluent, a brand name "Neothote E" (made by Toto Kasei Co., Ltd.) etc. can be mixed.

In addition, as a polyfunctional epoxy resin, "Finedic A-247S", "Finedic A-254", "Finedic A-253", "Finedic A-229-30A", "Finedic A-247S" manufactured by DIC Co., Ltd. Dick A-261”, “Finedic A249”, “Finedic A-266”, “Finedic A-241” “Finedic M-8020”, “Epicron N-740”, “Epicron N-770” , "Epicron N-865" (trade name), etc. can be used.

When a polyfunctional epoxy resin having a relatively small molecular weight is used as the thermosetting resin, epoxy groups are replenished in the ink composition (inkjet ink), the reaction point concentration of the epoxy becomes high, and the crosslinking density can be increased.

Among the polyfunctional epoxy resins, it is preferable to use an epoxy resin having 4 or more epoxy groups in one molecule (a tetrafunctional or higher functional epoxy resin) 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 from the ejection head in the inkjet method, the strength and hardness of the pixel portion (cured product of the ink composition) tend to decrease, so crosslinking From the viewpoint of sufficiently increasing the density, it is preferable to incorporate a tetrafunctional or higher functional epoxy resin into the ink composition (inkjet ink).

Examples of the curing agent and curing accelerator used for curing the thermosetting resin include 4-methylhexahydrophthalic anhydride, triethylenetetramine, diaminodiphenylmethane, phenol novolak resin, tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, triphenylphosphine, 3-phenyl-1,1-dimethylurea and the like.

The thermosetting resin may be alkali insoluble from the viewpoint of obtaining a highly reliable color filter pixel portion. That the thermosetting resin is insoluble in alkali means that the amount of dissolution of the thermosetting resin at 25°C in a 1% by mass aqueous solution of potassium hydroxide is 30% by mass or less based on the total mass of the thermosetting resin. The dissolution 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 is from the viewpoint of easily obtaining an appropriate viscosity as an inkjet ink, from the viewpoint of improving the curability of the ink composition, and from the viewpoint of improving the solvent resistance and wear resistance of the pixel portion (cured product of the ink composition), It may be 750 or more, 1000 or more, or 2000 or more. It may be 500,000 or less, 300,000 or less, or 200,000 or less from the viewpoint of setting the appropriate viscosity as inkjet ink. However, this is not the case for the molecular weight after crosslinking.

The content of the thermosetting resin is an ink composition from the viewpoint of easily obtaining an appropriate viscosity as an inkjet ink, from the viewpoint of improving the curability of the ink composition, and from the viewpoint of improving the solvent resistance and wear resistance of the pixel portion (cured product of the ink composition). It may be 10 mass% or more, 15 mass% or more, or 20 mass% or more based on the mass of the non-volatile matter of . The content of the thermosetting resin may be 90% by mass or less based on the mass of the non-volatile content of the ink composition, from the viewpoint that the viscosity of the inkjet ink does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function. , 80 mass % or less may be sufficient, 70 mass % or less may be sufficient, 60 mass % or less may be sufficient, and 50 mass % or less may be sufficient.

In this embodiment, the ink composition should just contain at least one of a photopolymerizable compound and a thermosetting resin, and may contain both a photopolymerizable compound and a thermosetting resin. The ink composition does not need to contain a thermosetting resin when it contains a photopolymerizable compound. In addition, when an ink composition contains a thermosetting resin, it is not necessary to contain a photopolymerizable compound. From the viewpoint of the storage stability of the ink composition containing the luminescent nanocrystal particles (eg, quantum dots) and the durability (moist heat stability, etc.) of the picture element portion (cured product of the ink composition), among photopolymerizable compounds and thermosetting resins, thermosetting It is preferable to use a resin, and from the viewpoint of the storage stability of the ink composition containing the luminescent nanocrystal particles (e.g., quantum dots) and the curing at a low temperature that is less susceptible to deterioration by heating of the quantum dots, the light It is more preferable to use a radically polymerizable compound, and it is preferable to use a photocationically polymerizable compound from the viewpoint of being able to form a picture element portion (cured product of the ink composition) without being subjected to oxygen inhibition in the curing process. .

When the ink composition contains a photopolymerizable compound and a thermosetting resin, the sum of the contents of the photopolymerizable compound and the thermosetting resin is the viewpoint of obtaining an appropriate viscosity as an inkjet ink, the viewpoint of improving the curability of the ink composition, and the pixel portion. From the viewpoint of improving the solvent resistance and abrasion resistance of the (cured product of the ink composition), the amount may be 3% by mass or more, 5% by mass or more, or 10% by mass or more based on the mass of the non-volatile matter of the ink composition. , 15 mass % or more may be sufficient, and 20 mass % or more may be sufficient. In addition, the sum of the contents of the photopolymerizable compound and the thermosetting resin is based on the mass of the non-volatile matter of the ink composition from the viewpoint that the viscosity of the inkjet ink does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function. Thus, it may be 80% by mass or less, 60% by mass or less, or 50% by mass or less.

The ink composition of the present embodiment can be applied as an ink used in a known and customary color filter manufacturing method, but it can be applied to a necessary location without wastefully consuming materials such as relatively expensive luminescent nanocrystal particles and solvents. Since the color filter pixel portion (photoconversion layer) can be formed only by using an amount required for the photolithography method, it is preferable to prepare and use it appropriately so as to be suitable for the inkjet 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 from the viewpoint 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, the meniscus shape of the ink composition at the tip of the ink ejection hole of the ejection head is stabilized, so that the ejection control of the ink composition (e.g., ejection amount and ejection amount) is stabilized. control of timing) becomes easy. On the other hand, when the viscosity is 20 mPa·s or less, the ink composition can be smoothly discharged from the ink discharge hole. The viscosity of the ink composition is 2 to 20 mPa s, 2 to 15 mPa s, 2 to 12 mPa s, 5 to 20 mPa s, 5 to 15 mPa 2 to 20 mPa s, 7 to 15 mPa s, and 7 to 12 mPa s. s, s, or 7 to 12 mPa·s may be sufficient. The viscosity of the ink composition is measured, for example, with an E-type viscometer.

The surface tension of the ink composition is preferably a surface tension suitable for an inkjet method, specifically preferably in the range of 20 to 40 mN/m, more preferably 25 to 35 mN/m. By setting the surface tension within the range, the occurrence of flight curvature can be suppressed. In addition, flight curvature means that the landing position of the ink composition shifts by 30 μm or more with respect to the target position when the ink composition is ejected from the ink ejection hole. When the surface tension is 40 mN/m or less, since the meniscus shape at the tip of the ink ejection hole is stable, ejection control of the ink composition (for example, control of ejection amount and ejection timing) becomes easy. On the other hand, when the surface tension is 20 mN/m or less, the occurrence of flight curvature can be suppressed. That is, a pixel portion in which the filling of the ink composition is insufficient occurs without accurately reaching the pixel portion formation region to be landed, or the ink composition lands on the pixel portion formation region (or pixel portion) adjacent to the pixel portion formation region to be landed. As a result, color reproducibility is not deteriorated.

The ink composition may further contain components other than luminescent nanocrystal particles, light-scattering particles, photopolymerizable compounds, thermosetting resins, polymerization initiators, and organic ligands within a range that does not impair the effects of the present invention. As another component, a polymer dispersing agent, a sensitizer, a solvent, etc. are mentioned, for example.

[Polymer Dispersant]

In the present invention, the polymeric dispersing agent is a polymeric 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 light-scattering particles. The polymer dispersant is adsorbed to the light scattering particles via a functional group having affinity for the light scattering particles, and the light scattering particles are formed in the ink composition by electrostatic repulsion and/or steric repulsion between the polymer dispersants. dispersed among The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may be bonded to the surface of the luminescent nanocrystal particles and adsorbed to the luminescent nanoparticles, or may be free in the ink composition. do.

However, in the case of forming a color filter pixel portion by an inkjet method using a conventional ink composition, the stability of ejection from an inkjet nozzle may decrease due to aggregation of luminescent nanocrystal particles and light scattering particles. Further, it is conceivable that the ejection stability is improved by miniaturizing the luminescent nanocrystal particles and the light scattering particles, or by reducing the content of the luminescent nanocrystal particles and the light scattering particles, etc. In this case, the effect of reducing the leakage light is reduced. It was easy to do, and it was difficult to achieve both sufficient discharge stability and the effect of reducing leakage light. On the other hand, according to the ink composition further containing a polymeric dispersant, leaking light can be further reduced while ensuring sufficient ejection stability. Although the reason why such an effect is obtained is not clear, it is guessed that it is because aggregation of luminescent nanocrystal particle|grains and light-scattering particle|grains (particularly light-scattering particle|grains in particular) is remarkably suppressed by a polymer dispersing agent.

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

Examples of the acidic functional group include a carboxy group (-COOH), a sulfo group (-SO ₃ H), a sulfate group (-OSO ₃ H), a phosphonic acid group (-PO(OH) ₃ ), a phosphoric acid group (-OPO(OH) ₃ ), and a phosphate group. A pinic acid group (-PO(OH)-) and a mercapto group (-SH) are exemplified.

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

Examples of the nonionic functional group include a hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO ₂ -), a carbonyl group, a formyl group, an ester group, a carbonate ester group, an amide group, a carbamoyl group, A ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group, and a phosphine sulfide group are mentioned.

From the viewpoint of the dispersion stability of the light scattering particles, the difficulty of causing the side effect of sedimentation of the luminescent nanocrystal particles, the ease of synthesis of the polymer dispersant, and the stability of the functional group, as the acidic functional group, a carboxy group, a sulfo group, a phosphone group An acid group and a phosphoric acid group are preferably used, and an amino group is preferably used as the basic functional group. Among these, a carboxyl group, a phosphonic acid group, and an amino group are more preferably used, and an amino group is most preferably used.

The polymeric dispersing agent having an acidic functional group has an acid value. The acid value of the polymer dispersing agent having an acidic functional group is preferably 1 to 150 mgKOH/g in terms of solid content. When the acid value is 1 or more, sufficient dispersibility of the light scattering particles is easily obtained, and when the acid value is 150 or less, the storage stability of the pixel portion (cured product of the ink composition) is difficult to decrease.

In addition, the polymeric dispersing agent having a basic functional group has an amine value. The amine value of the polymer dispersing agent 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, sufficient dispersibility of the light-scattering particles is easily obtained, and when the amine value is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) is difficult to decrease.

The polymer dispersing agent may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of a plurality of types of monomers. Moreover, any of a random copolymer, a block copolymer, or a graft copolymer may be sufficient as a polymeric dispersing agent. Further, when the polymer dispersing agent is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. Polymer dispersants include, for example, acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyethers, phenolic resins, silicone resins, polyurea resins, amino resins, polyamines such as polyethyleneimine and polyarylamine, epoxies Resin, polyimide, etc. may be sufficient.

As the above-mentioned polymer dispersant, it is also possible to use a commercial product, and as a commercial product, Ajinomoto Fine Techno Co., Ltd.'s Ajispa PB series, BYK's DISPERBYK series and BYK-series, BASF's Efka series, etc. can be used.

As a commercial item, for example, "DISPERBYK-130", "DISPERBYK-161", "DISPERBYK-162", "DISPERBYK-163", "DISPERBYK-164", "DISPERBYK-166", "DISPERBYK-166" made by Big Chemie Co., Ltd. 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-LPN21116" LPN6919”; "EFKA4010", "EFKA4015", "EFKA4046", "EFKA4047", "EFKA4061", "EFKA4080", "EFKA4300", "EFKA4310", "EFKA4320", "EFKA4330", "EFKA4340", "EFKA4560" manufactured by BASF , "EFKA4585", "EFKA5207", "EFKA1501", "EFKA1502", "EFKA1503" and "EFKA PX-4701"; 「Solpas 3000」, 「Solpas 9000」, 「Solspas 13240」, 「Solspas 13650」, 「Solspas 13940」, 「Solspas 11200」, 「Solspas 11200」, 「Solspas」 manufactured by Lubrizol 13940”, “Solspas 16000”, “Solspas 17000”, “Solspas 18000”, “Solspas 20000”, “Solspas 21000”, “Solspas 24000”, “Solspas 26000”, “Solspas 27000”, “Solspas 28000”, “Solspas 32000”, “Solspas 32500”, “Solspas 32550”, “Solspas 32600”, “Solspas 33000 ”, “Solpas 34750”, “Solspas 35100”, “Solspas 35200”, “Solspas 36000”, “Solspas 37500”, “Solspas 38500”, “Solspas 39000” , "Solpas 41000", "Solpas 54000", "Solpas 71000" and "Solpas 76500"; "Ajispa PB821", "Ajispa PB822", "Ajispa PB881", "PN411" and "PA111" by Ajinomoto Fine Techno Co., Ltd.; "TEGO Dispers650", "TEGO Dispers660C", "TEGO Dispers662C", "TEGO Dispers670", "TEGO Dispers685", "TEGO Dispers700", "TEGO Dispers710" and "TEGO Dispers760W" manufactured by Evonik; "Disparon DA-703-50", "DA-705", "DA-725", etc. made by Kusumoto Chemical can be used.

As the polymer dispersant, in addition to the above commercial products, a cationic monomer containing a basic group and/or an anionic monomer having an acidic group, a monomer having a hydrophobic group, and other monomers (nonionic monomers, monomers having a hydrophilic group, etc.) as necessary A compound synthesized by copolymerization may be used. About the details of a cationic monomer, an anionic monomer, the monomer which has a hydrophobic group, and another monomer, the monomer of Unexamined-Japanese-Patent No. 2004-250502 Paragraph 0034-0036 is mentioned.

Further, compounds obtained by reacting a polyalkyleneimine with a polyester compound disclosed in, for example, Japanese Patent Laid-Open No. 54-37082, Japanese Patent Laid-Open No. 61-174939, etc., Japanese Patent Laid-Open No. 9-169821 A compound obtained by modifying the amino group of the side chain of polyarylamine described with polyester; a graft polymer having a polyester type macromonomer as a copolymerization component described in Japanese Patent Laid-Open No. 9-171253; The polyester polyol addition polyurethane described in , etc. are mentioned suitably.

The weight average molecular weight of the polymeric dispersant may be 750 or more, 1000 or more, 2000 or more, or 3000 or more from the viewpoint of being able to favorably disperse light scattering particles and further improving the effect of reducing light leakage. do. The weight average molecular weight of the polymeric dispersant can favorably disperse the light scattering particles, can further improve the effect of reducing light leakage, and also makes the viscosity of the inkjet ink capable of ejection and suitable for stable ejection From the viewpoint, 100000 or less may be sufficient, 50000 or less may be sufficient, and 30000 or less may be sufficient. In the present specification, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography).

The content of the polymeric dispersant may be 0.5 parts by mass or more, 2 parts by mass or more, or 5 parts by mass or more with respect to 100 parts by mass of the light-scattering particles from the viewpoint of the dispersibility of the light-scattering particles. The content of the polymer dispersion may be 50 parts by mass or less, 30 parts by mass or less, or 10 parts by mass or less with respect to 100 parts by mass of the light scattering particles from the viewpoint of wet heat stability of the picture element portion (cured product of the ink composition). do.

[sensitizer]

As the sensitizer, photopolymerizable compounds and thermosetting resins and amines that do not cause an addition reaction can be used. Examples of the sensitizer include trimethylamine, methyl dimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and N,N-dimethylbenzylamine. , 4,4'-bis (diethylamino) benzophenone, etc. are mentioned.

[solvent]

Examples of the solvent include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, Diethyl malonate, dimethyl succinate, diethyl succinate, 1,4-butanediol diacetate, glyceryl triacetate, etc. are mentioned.

It is preferable that the boiling point of a solvent is 180 degreeC or more from a viewpoint of continuous ejection stability of inkjet ink. Further, since it is necessary to remove the solvent from the ink composition before curing the ink composition when forming the pixel portion, the boiling point of the solvent is preferably 300°C or less from the viewpoint of easy removal of the solvent.

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

As mentioned above, although one embodiment of the ink composition for color filters was described, the ink composition of the above-mentioned embodiment can also be used by a photolithographic method other than the inkjet method. In this case, the ink composition contains an alkali-soluble resin as a binder polymer.

When the ink composition is used in a photographic manner, first, the ink composition is applied onto a substrate, and when the ink composition contains a solvent, the ink composition is further dried to form a coating film. The coated film obtained in this way is soluble in an alkaline developer, and is patterned by being treated with an alkaline developer. At this time, since most of the alkaline developing solution is an aqueous solution from the viewpoint of the ease of wastewater treatment of the developing solution, the coated film of the ink composition is treated with an aqueous solution. On the other hand, in the case of an ink composition using luminescent nanocrystal particles (e.g., quantum dots), the luminescent nanocrystal particles are unstable to water, and luminescence (eg, fluorescence) is impaired by moisture. For this reason, in this embodiment, the inkjet method which does not need to process with an alkaline developing solution (aqueous solution) is preferable.

In addition, even when the coating film of the ink composition is not treated with an alkali developer, when the ink composition is alkali-soluble, the coating film of the ink composition easily absorbs moisture in the air, and as time passes, the luminescent nanocrystals Luminescence (for example, fluorescence) of particles (quantum dots, etc.) is impaired. From this point of view, in the present embodiment, it is preferable that the coating film of the ink composition is alkali insoluble. That is, it is preferable that the ink composition of this embodiment is an ink composition which can form 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. That the coating film of the ink composition is insoluble in alkali means that the dissolution amount of the coating film of the ink composition at 25 ° C. with respect to 1% by mass of potassium hydroxide aqueous solution is 30% by mass or less based on the total mass of the coating film of the ink composition do. The dissolution amount of the coated film of the ink composition is preferably 10% by mass or less, and more preferably 3% by mass or less. In addition, the reason why the ink composition is an ink composition capable of forming an alkali-insoluble coating film is that the coating film having a thickness of 1 μm obtained by applying the ink composition on a substrate and then drying under conditions of 80 ° C. for 3 minutes, including a solvent, It can be confirmed by measuring the amount of dissolution.

<Method for producing ink composition>

Next, the manufacturing method of the ink composition of the above-mentioned embodiment is demonstrated. The ink composition is obtained, for example, by mixing the components of the ink composition described above and performing a dispersion treatment. Below, as an example of the manufacturing method of an ink composition, the manufacturing method of the ink composition containing a polymer dispersing agent is demonstrated.

A 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 a step of mixing the dispersion of light-scattering particles and luminescent nanocrystal particles. It is equipped with 2 processes. In this method, the dispersion of light scattering particles may further contain a photopolymerizable compound and/or a thermosetting resin, and in the second step, the photopolymerizable compound and/or the thermosetting resin may be further mixed. According to this method, light-scattering particles can be sufficiently dispersed. Therefore, while being able to reduce light leakage in a pixel part, an ink composition excellent in ejection stability can be obtained easily.

In the step of preparing the dispersion of light-scattering particles, the dispersion of light-scattering particles is obtained by mixing the light-scattering particles, the polymer dispersant, and optionally the photopolymerizable compound and/or the thermosetting resin, and performing dispersion treatment. may be prepared. The mixing and dispersion treatment may be performed using a dispersion device such as a bead mill, a paint conditioner, or a planetary agitator. It is preferable to use a bead mill or paint conditioner from the viewpoint that the dispersibility of the light-scattering particles becomes good and the average particle diameter of the light-scattering particles can be easily adjusted to a desired range.

The method for producing an ink composition may further include, before the second step, a step of preparing a dispersion of luminescent nanocrystal particles containing luminescent nanocrystal particles, a photopolymerizable compound, and/or a thermosetting resin. In this case, in the second step, the dispersion of light scattering particles and the dispersion of luminescent nanocrystal particles are mixed. According to this method, the luminescent nanocrystal particles can be sufficiently dispersed. Therefore, while being able to reduce light leakage in a pixel part, an ink composition excellent in ejection stability can be obtained easily. In the step of preparing the dispersion of luminescent nanocrystal particles, using the same dispersing device as in the step of preparing the dispersion of light-scattering particles, the luminescent nanocrystal particles, the photopolymerizable compound, and/or the thermosetting resin are mixed with each other. Mixing and dispersing treatment may be performed.

When using the ink composition of this embodiment as an ink composition for an inkjet system, it is preferably applied to a piezojet system inkjet recording apparatus using a mechanical ejection mechanism using a piezoelectric element. In the piezojet method, in ejection, the ink composition is not instantly exposed to high temperatures, and the luminescent nanocrystal particles are less likely to deteriorate, and the color filter pixel portion (light conversion layer) also has the expected light emitting characteristics more easily. easy to obtain

<Light conversion layer and color filter>

Next, details of the photo conversion layer and color filter using the ink composition of the above-described embodiment will be described with reference to the drawings. In addition, in the following description, the same code|symbol is used for the same or equivalent element, and overlapping description is abbreviate|omitted.

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 substrate 40 and a light conversion layer 30 provided on the substrate 40 . The light conversion layer 30 includes a plurality of pixel units 10 and a light blocking unit 20 .

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

The 1st pixel part 10a and the 2nd pixel part 10b each contain the hardened|cured material of the ink composition of the above-mentioned embodiment. The cured product contains luminescent nanocrystal particles, light scattering particles, and a curing component. The curing component is a cured product of a photopolymerizable compound and/or a thermosetting resin, specifically, a cured product obtained by polymerization of a photopolymerizable compound and/or crosslinking of a thermosetting resin. That is, the first pixel portion 10a includes the first curing component 13a, the first luminescent nanocrystal particles 11a and the first light scattering particles 12a respectively dispersed in the first curing component 13a. include Similarly, the second pixel portion 10b includes the second curing component 13b, the second luminescent nanocrystal particles 11b and the second light scattering particles 12b respectively dispersed in the second curing component 13b. include In the first pixel portion 10a and the second pixel portion 10b, the first curing component 13a and the second curing component 13b may be the same or different, and the first light scattering particles 12a and the second curing component 13b The light scattering particles 12b may be the same or different.

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

The content of the luminescent nanocrystal particles in the pixel portion including the cured product of the ink composition may be 5% by mass or more based on the total mass of the cured product of the ink composition, from the viewpoint of a more excellent effect of reducing leakage light, 10 mass % or more may be sufficient, 15 mass % or more may be sufficient, 20 mass % or more may be sufficient, 30 mass % or more may be sufficient, and 40 mass % or more may be sufficient. The content of the luminescent nanocrystal particles may be 70% by mass or less, may be 60% by mass or less, may be 55% by mass or less, based on the total mass of the cured product of the ink composition, from the viewpoint of excellent reliability of the pixel portion, 50 It may be less than mass %.

The content of the light-scattering particles in the pixel portion including the cured product of the ink composition may be 0.1% by mass or more based on the total mass of the cured product of the ink composition, from the viewpoint of a more excellent effect of reducing leakage light, and is 1 It may be mass % or more, 5 mass % or more, 7 mass % or more, 10 mass % or more, or 12 mass % or more may be sufficient. The content of the light-scattering particles may be 60% by mass or less, and may be 50% by mass or less, based on the total mass of the cured product of the ink composition, from the viewpoint of a more excellent light leakage reduction effect and excellent reliability of the pixel portion, 40 mass % or less may be sufficient, 30 mass % or less may be sufficient, 25 mass % or less may be sufficient, 20 mass % or less may be sufficient, and 15 mass % or less may be sufficient.

The third pixel portion 10c has a transmittance of 30% or more to light having a wavelength in the range of 420 to 480 nm. Therefore, the third pixel portion 10c functions as a blue pixel portion when a light source emitting light with a wavelength in the range of 420 to 480 nm is used. The 3rd pixel part 10c contains the hardened|cured material of the composition containing the photopolymerizable compound and/or the thermosetting resin mentioned above, for example. The cured product contains the third cured component 13c. The third curing component 13c is a cured product of a photopolymerizable compound and/or a thermosetting resin, specifically, a cured product obtained by polymerization of a photopolymerizable compound and/or crosslinking of a thermosetting resin. That is, the third pixel portion 10c includes the third curing component 13c. When the third pixel portion 10c includes the cured product described above, the composition containing the photopolymerizable compound and/or the thermosetting resin has a transmittance of 30% or more to light having a wavelength in the range of 420 to 480 nm. Among the components contained in the above-described ink composition, components other than the photopolymerizable compound and the thermosetting resin may be further contained within the limit that is specified. In addition, the transmittance of the third pixel portion 10c can be measured by a microscopy device.

The thickness of the pixel portions (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. may be continued The thickness of the pixel portions (the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c) may be, for example, 30 μm or less, 20 μm or less, or 15 μm or less. may be

The light blocking unit 20 is a so-called black matrix provided for the purpose of preventing color mixing by separating adjacent pixel units and preventing light leakage from a light source. The material constituting the light-shielding portion 20 is not particularly limited, and a cured product of a resin composition in which light-blocking particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are incorporated in a binder polymer in addition to metals such as chromium, etc. can be used. Examples of the binder polymer used herein include resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, etc., alone or in combination of two or more, photosensitive resin, O/ A resin composition of a W emulsion type (for example, one obtained by emulsifying a reactive silicone) or the like can be used. The thickness of the light-shielding portion 20 may be, for example, 0.5 μm or more and 10 μm or less.

The substrate 40 is a transparent substrate having light transmission, for example, a transparent glass substrate such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz plate, a transparent flexible substrate such as a transparent resin film, or a resin film for optics. etc. can be used. Among these, it is preferable to use the glass substrate which consists of an alkali-free glass which does not contain an alkali component in glass. Specifically, "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" made by Corning, "AN100" made by Asahi Glass, "OA-10G" and "OA" made by Nippon Denki Glass Co., Ltd. -11” is suitable. These are materials with a small coefficient of thermal expansion and are excellent in dimensional stability and workability in high-temperature heat treatment.

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

The color filter 100 is, for example, formed in a pattern on the base material 40, after forming the light blocking portion 20, in the pixel portion formation area partitioned by the light blocking portion 20 on the base material 40, It can be produced by a method of selectively adhering the ink composition (inkjet ink) of the above-described embodiment by an inkjet method and curing the ink composition by irradiation with active energy rays or heating.

A method of forming the light-shielding portion 20 is to form a metal thin film such as chromium or a thin film of a resin composition containing light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one side of a substrate 40. and a method of patterning this thin film. The metal thin film can be formed by, for example, sputtering or vacuum deposition, and the thin film of a resin composition containing light-shielding particles can be formed by, for example, coating or printing. A photolithography method etc. are mentioned as a method of patterning.

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

When curing the ink composition by irradiation with active energy rays (eg, ultraviolet rays), you may use, for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED or the like. The wavelength of light to be irradiated 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 4000 mJ/cm 2 or less.

When curing the ink composition 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 longer and 120 minutes or shorter.

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

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

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

Further, the color filter may include an ink repellent layer made of a material having ink repellent properties narrower than the light shield portion on the pattern of the light shielding portion. In addition, instead of providing an ink repellent layer, a photocatalyst-containing layer as a variable wettability layer is formed in a solid coated form in a region including a pixel portion formation region, and then the photocatalyst-containing layer is exposed by irradiating light through a photomask. may be performed to selectively increase the ink affinity of the pixel portion formation region. As a photocatalyst, titanium oxide etc. are mentioned.

Further, the color filter may include an ink receiving layer made of hydroxypropyl cellulose or the like between the substrate and the pixel portion.

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

In addition, in manufacture of a color filter and a photo conversion layer, you may form a pixel part not by an inkjet method but by a photolithography method. In this case, first, the ink composition layer is formed by applying the ink composition to the base material in layers. Then, after the ink composition layer is exposed in a pattern, it is developed using a developing solution. In this way, the picture element part which consists of a hardened|cured material of an ink composition is formed. Since the developing solution is usually alkaline, an alkali-soluble polymer is used as the binder polymer. However, the inkjet method is superior to the photolithography method in terms of material use efficiency. This is because the photolithography method, in principle, removes approximately 2/3 or more of the material, and the material is wasted. For this reason, in this embodiment, it is preferable to form the pixel part by an inkjet method using inkjet ink.

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

In addition, among the red pixel portion (R), the green pixel portion (G), and the blue pixel portion (B) in the light conversion layer of the present embodiment, one or both do not contain luminescent nanocrystal particles but contain a colorant. It is good also as a made-up pixel part. As the color material usable here, a known color material can be used, and examples of the color material used for the red pixel portion R include diketopyrrolopyrrole pigments and/or anionic red organic dyes. As the color material used for the green pixel portion G, at least one selected from the group consisting of a halogenated copper phthalocyanine pigment, a phthalocyanine-based green dye, a mixture of a phthalocyanine-based blue dye and an azo-based yellow organic dye can be exemplified. have. Examples of the color material used for the blue pixel portion (B) include an ε-type copper phthalocinian pigment and/or a cationic blue organic dye. The amount of these colorants, when contained in the light conversion layer, is 1 to 5% by mass based on the total mass of the pixel portion (cured product of the ink composition) from the viewpoint of preventing a decrease in transmittance. desirable.

[Example]

Hereinafter, the present invention will be described in detail according to examples. However, the present invention is not limited only to the following examples.

In Examples and Comparative Examples, the following materials were used.

[Luminescent nanocrystal particles]

QD Dispersion 1: 776785

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

QD Dispersion 2: 776750

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

[Light Scattering Particles]

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

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

[Photopolymerizable Compound]

- Alicyclic epoxy monomer: Celoxide 2000 (trade name of Daisel Co., Ltd., "Celoxide" is a registered trademark)

・Oxetane monomer: Aaron oxetane OXT-212 (trade name of Toagosei Co., Ltd., “Aron oxetane” is a registered trademark)

[Polymer Dispersant]

・Polymer dispersing agent: 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 the QD dispersion 1 and 8 g of the alicyclic epoxy monomer, by removing toluene derived from the QD dispersion with an evaporator, QD / alicyclic epoxy monomer dispersion 1 (QD content: 20% by mass) got it

(Preparation Example 2)

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

<Preparation of Light Scattering Particle Dispersion>

(Preparation Example 3)

1.29 g of titanium oxide 1, 0.13 g of a polymer dispersant, and 1.81 g of an oxetane monomer were blended. After adding zirconia beads (diameter: 5 mm) to the obtained formulation, dispersion treatment of the formulation was performed by shaking for 2 hours using a paint conditioner. In this way, a light-scattering particle dispersion 1 was obtained.

(Preparation Example 4)

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

(Preparation Example 5)

A light-scattering particle dispersion 3 was obtained in the same manner as in Preparation Example 3 except that the dispersion treatment of the blend was performed by stirring for 5 minutes at 2000 rpm using a planetary stirrer (trade name "ARE-310" manufactured by Shinki Co., Ltd.). .

(Preparation Example 6)

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

(Preparation Example 7)

1.31 g of titanium oxide 1 and 1.83 g of oxetane monomer were blended. After adding zirconia beads (diameter: 5 mm) to the obtained formulation, dispersion treatment of the formulation was performed by shaking for 2 hours using a paint conditioner. In this way, light-scattering particle dispersion 5 was obtained.

(Preparation Example 8)

A light-scattering particle dispersion 6 was obtained in the same manner as in Preparation 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 the QD/alicyclic epoxy monomer dispersion 1, 3.23 g of the light scattering particle dispersion 1, and 0.3 g of a photocationic polymerization initiator, the mixture was filtered through a filter having a pore size of 5 μm. , an ink composition was obtained. The average particle diameter (volume average diameter MV) of the light-scattering particles in the ink composition was 0.35 µm. In the present embodiment, the average particle diameter (volume average diameter MV) of the light scattering particles in the ink composition is determined by using a dynamic light scattering type nanotrack particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., trade name "Nanotrack") was measured.

(2) Fabrication of light conversion filter

The ink composition obtained in the above (1) was applied onto a glass substrate (slide glass) by a spin coater so that the film thickness after drying was 5 µm. After drying the obtained film, ultraviolet rays were irradiated to the film after drying at an exposure amount of 2000 mJ/cm 2 . Thus, the ink composition was cured to form a layer (light conversion layer) made of a cured product of the ink composition on the glass substrate. A light conversion filter was obtained by the above operation.

(3) Evaluation

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

[Leak Light Evaluation]

As a surface emission light source, a blue LED (peak emission wavelength: 450 nm) manufactured by CCS Co., Ltd. was used. On this light source, a light conversion filter was installed with the glass substrate side facing downward. An integrating sphere was connected to a radiation spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (trade name "MCPD-9800"), and the integrating sphere was brought close to a light conversion filter installed on a blue LED. In this state, the blue LED was turned on, and the peak intensity (S) of the observed light having a wavelength of 450 nm was measured. Next, instead of the light conversion filter, except that the glass substrate (slide glass) used for the production of the light conversion filter was installed on the light source, the same method was performed as described above to observe light having a wavelength of 450 nm, and Peak intensity (R) was measured. The leak 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, the higher the color purity, which is preferable.

A: T<20%

B: 20≤T≤50%

C: T>50%

[Discharge stability evaluation]

The ink composition was continuously discharged for 10 minutes using an inkjet printer (manufactured by Fujifilm Dimatix, trade name "DMP-2831"). In addition, 16 nozzles are formed in the head part which ejects ink of this inkjet printer, and the usage-amount of the ink composition per nozzle per discharge was 10 pL. Discharge stability was evaluated according to the following criteria.

A: Continuous discharge possible (out of 16 nozzles, continuous discharge is possible with 10 or more nozzles)

B: Unable to discharge continuously (out of 16 nozzles, the number of nozzles capable of continuous discharge is 9 nozzles or less)

C: dispensing impossible

(Example 2)

An ink composition was obtained in the same manner as in Example 1, except for using the light-scattering particle dispersion 2 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 this ink composition was used. Using the obtained ink composition and light conversion filter, it was carried out similarly to Example 1, and light leakage evaluation and ejection stability evaluation were performed. 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 this ink composition was used. Using the obtained ink composition and light conversion filter, it was carried out similarly to Example 1, and light leakage evaluation and ejection stability evaluation were performed. 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 this ink composition was used. Using the obtained ink composition and light conversion filter, it was carried out similarly to Example 1, and light leakage evaluation and ejection stability evaluation were performed. 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 this ink composition was used. Using the obtained ink composition and light conversion filter, it was carried out similarly to Example 1, and light leakage evaluation and ejection stability evaluation were performed. The results are shown in Table 1.

(Example 6)

Examples except that 6.55 g of QD/alicyclic epoxy monomer dispersion 1 was used, 3.14 g of light scattering particle dispersion 5 was used instead of light scattering particle dispersion 1, and 0.31 g of photocationic polymerization initiator was used. In the same manner as in 1, an ink composition was obtained. 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 this ink composition was used. Using the obtained ink composition and light conversion filter, it was carried out similarly to Example 1, and light leakage evaluation and ejection stability evaluation were performed. 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 this ink composition was used. Using the obtained ink composition and light conversion filter, it was carried out similarly to Example 1, and light leakage evaluation and ejection stability evaluation were performed. The results are shown in Table 1.

(Comparative Example 1)

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

[Table 1]

As shown in Table 1, when the ink composition of Comparative Example 1 in which light scattering particles were not used was used, it was confirmed that light leakage was remarkable. In addition, as shown in Table 1, in the ink compositions of Examples 1 and 2, in which light scattering particles are dispersed by a paint conditioner using a polymer dispersant and the particle size is smaller than 1.0 μm, the polymer dispersant is used, but oil-based. The ink compositions of Examples 4 and 5 having a particle size larger than 1.0 μm and the light-scattering particles are dispersed using a paint conditioner, but a polymer dispersant is not used and the particle size is smaller than 1.0 μm. It was confirmed that the ejection stability superior to that of the ink compositions of Examples 6 and 7 was obtained.

(Example 8)

First, a substrate (BM substrate) having a light-shielding portion called a black matrix (BM) was fabricated by the following procedure. That is, after applying a black resist ("CFPR BK" manufactured by Tokyo Oka Kogyo Co., Ltd.) on a glass substrate made of alkali-free glass ("OQ-10G" manufactured by Nippon Denki Glass Co., Ltd.), pattern exposure, development, and baking are performed. By doing so, a patterned light-shielding portion was formed. Exposure was performed by irradiating ultraviolet rays with an exposure amount of 200 mJ/cm 2 to the black resist. The pattern of the light-shielding portion was a pattern having openings corresponding to sub-pixels of 200 µm x 600 µm, and had a line width of 20 µm and a thickness of 2.6 µm.

Next, after printing the ink composition obtained in Example 1 on the openings on the BM substrate by an inkjet method, ultraviolet rays were irradiated. It was then heated at 150°C for 30 minutes under a nitrogen atmosphere. In this way, the ink composition was cured to form a picture element portion composed of a cured product of the ink composition. The resulting pixel portion is a pixel portion that converts blue light into red light. The thickness of the pixel portion was 2.1 μm. By the above operation, a photoconversion filter with a pattern was obtained.

(Example 9)

In the same manner as in Example 8, a BM substrate was prepared. Then, the ink composition obtained in Example 1 and the ink composition obtained in Example 3 were printed on the openings on the BM substrate by an inkjet method, and then ultraviolet rays were irradiated to cure the ink compositions. Thus, on the BM substrate, a pixel unit for converting blue light into red light and a pixel unit for converting blue light into green light were formed. Through the above operation, a photoconversion filter with a pattern provided with a plurality of types of pixel parts was obtained.

10: pixel part
10a: first pixel unit
10b: second pixel unit
10c: third pixel unit
11a: first luminescent nanocrystal particle
11b: second luminescent nanocrystal particles
12a: first light scattering particles
12b: second light scattering particles
20: light blocking part
30: light conversion layer
40: base
100: color filter

Claims (23)

Luminescent nanocrystal particles;
light-scattering particles;
A photopolymerizable compound and/or a thermosetting resin;
An ink composition containing a polymer dispersant,
The content of the luminescent nanocrystal particles is 10 to 50% by mass based on the mass of the non-volatile matter of the ink composition,
The acid value of the polymer dispersant is 1 to 150 mgKOH / g,
An ink composition for forming a pixel portion of a color filter. According to claim 1,
The weight average molecular weight of the polymer dispersant is 1000 or more ink composition. According to claim 1 or 2,
The ink composition wherein the photopolymerizable compound is a photoradical polymerizable compound. According to claim 1 or 2,
The ink composition wherein the photopolymerizable compound is a photocationically polymerizable compound. According to claim 1 or 2,
The ink composition wherein the photopolymerizable compound is alkali insoluble. According to claim 1 or 2,
The ink composition wherein the thermosetting resin is alkali insoluble. According to claim 1 or 2,
An ink composition capable of forming an alkali-insoluble coating film. According to claim 1 or 2,
The ink composition wherein the light scattering particles have an average particle diameter of 0.05 to 1.0 μm. According to claim 1 or 2,
The ink composition wherein the light scattering particles have an average particle diameter of 0.3 to 0.6 μm. According to claim 1 or 2,
wherein the light-scattering particles contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silica. According to claim 1 or 2,
An ink composition having a surface tension of 20 to 40 mN/m. According to claim 1 or 2,
An ink composition having a viscosity of 2 to 20 mPa·s. According to claim 1 or 2,
An ink composition further containing a solvent having a boiling point of 180°C or higher. delete According to claim 1 or 2,
An ink composition used in an inkjet method. As a light conversion layer having a plurality of pixel units,
A light conversion layer having a pixel portion, wherein the plurality of pixel portions include a cured product of the ink composition according to claim 1 or 2. According to claim 16,
Further comprising a light blocking portion provided between the plurality of pixel portions,
The plurality of pixel units,
containing the cured product, and further containing, as the luminescent nanocrystal particles, luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a peak emission wavelength in the range of 605 to 665 nm a first pixel unit;
containing the cured product, and further containing, as the luminescent nanocrystal particles, luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a peak emission wavelength in the range of 500 to 560 nm , the second pixel unit
A light conversion layer having a. According to claim 17,
The plurality of pixel units, the light conversion layer further comprising a third pixel unit having a transmittance of 30% or more for light having a wavelength in the range of 420 to 480 nm. A color filter comprising the light conversion layer according to claim 16. delete delete delete delete

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