CN117777785A - Light scattering ink composition, light scattering laminated substrate, backlight unit, light scattering pixel substrate, and image display device - Google Patents
Light scattering ink composition, light scattering laminated substrate, backlight unit, light scattering pixel substrate, and image display device Download PDFInfo
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- CN117777785A CN117777785A CN202311174061.5A CN202311174061A CN117777785A CN 117777785 A CN117777785 A CN 117777785A CN 202311174061 A CN202311174061 A CN 202311174061A CN 117777785 A CN117777785 A CN 117777785A
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- light scattering
- scattering
- ink composition
- light
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- 238000000149 argon plasma sintering Methods 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000000758 substrate Substances 0.000 title claims abstract description 53
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 19
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
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- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- 238000013007 heat curing Methods 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
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- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a light scattering ink composition, a light scattering laminated substrate, a backlight unit, a light scattering pixel substrate, and an image display device, which have excellent physical properties, wherein the light scattering ink composition comprises first scattering particles, second scattering particles, a photopolymerizable compound, and a photopolymerization initiator, the first scattering particles have an average particle diameter of more than 100nm and less than 350nm, the second scattering particles have an average particle diameter of more than 40nm and less than 400nm, and the first scattering particles are selected from titanium oxide (TiO 2 ) Zinc oxide (ZnO), silicon oxide (SiO) 2 ) Barium sulfate (BaSO) 4 ) Zirconia (ZrO) 2 ) At least one of the group consisting of the second scattering particles is an organic particle.
Description
Technical Field
The invention relates to a light scattering ink composition, a light scattering laminated substrate manufactured by using the same, a light scattering pixel substrate and an image display device.
Background
Recently, as one of methods for realizing a color filter of an image display device, a pigment dispersion method using a pigment dispersion type photosensitive resin is adopted. However, light irradiated from the light source is partially absorbed by the color filter during the process of passing through the color filter, which results in a decrease in light efficiency, and there is a problem in that color reproducibility is decreased due to the characteristics of the pigment contained in the color filter. Color reproduction rate is one of the most important elements in a display device. In recent years, as an example of a means for improving the color reproduction rate of a display device, a display device is used which uses blue LEDs instead of normal white LEDs and which includes a light scattering laminated substrate including quantum dots (quantum dots) as individual light conversion means. However, in the case of including quantum dots, efficiency of quantum dots, particularly efficiency of blue quantum dots, is lowered, and thus performance of a display device is lowered, and price of blue quantum dots is high, so there is a problem that overall manufacturing cost is increased. For this purpose, a pixel substrate has been proposed that uses a light source that emits blue light, a red pattern layer containing red quantum dot particles and a green pattern layer containing green quantum dot particles, and that includes a transparent pattern layer containing no quantum dot particles at positions corresponding to the blue pattern layer, whereby the red quantum dot particles emit red light and the green quantum dot particles emit green light, and the transparent pattern layer directly transmits the blue light to display blue. In order to ensure uniformity of transmitted light, such a transparent pattern layer contains scattering particles instead of quantum dots.
In korean registered patent publication No. 10-1764478, it is desired to provide a color conversion film excellent in brightness, uniformity, etc. of emitted light by laminating one or more layers of scattering particles in a color conversion layer provided on a transparent substrate and a light scattering layer provided on the color conversion layer. However, since the diameter of the plurality of scattering particles is 0.7 μm to 5 μm, there is a problem of sedimentation in the composition, and there is a problem of poor ejection properties when produced by an inkjet method.
Prior art literature
Patent literature
Patent document 1: korean registered patent publication No. 10-1764478
Disclosure of Invention
Problems to be solved
In order to solve the above problems, an object of the present invention is to provide a light scattering ink composition having excellent light efficiency and excellent physical properties such as stability and adhesion.
The present invention also provides a light scattering ink composition which is excellent in ejection characteristics and can be easily produced by an inkjet method.
Further, an object of the present invention is to provide a light scattering laminated substrate, a light scattering pixel substrate, and an image display device manufactured using the light scattering ink composition.
However, the problems to be solved by the present application are not limited to the above-mentioned problems, and other problems not mentioned should be understood by those skilled in the art from the following description.
Means for solving the problems
The present invention relates to a light scattering ink composition comprising first scattering particles, second scattering particles, a photopolymerizable compound, and a photopolymerization initiator, wherein the first scattering particles have an average particle diameter of more than 100nm and less than 350nm, the second scattering particles have an average particle diameter of more than 40nm and less than 400nm, and the first scattering particles are selected from the group consisting of titanium oxide (TiO 2 ) Zinc oxide (ZnO), silicon oxide (SiO) 2 ) Barium sulfate (BaSO) 4 ) Zirconia (ZrO) 2 ) At least one of the group consisting of the second scattering particles is an organic particle.
In the present invention, the first scattering particles may have an average particle diameter of 150nm to 300nm, and the second scattering particles may have an average particle diameter of 50nm to 350 nm.
In the present invention, the organic particles may be at least one selected from the group consisting of polymethyl methacrylate particles, acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, acrylic-styrene copolymer particles, melamine particles, crosslinked melamine particles, benzoguanamine resin particles, polycarbonate particles, polyvinyl chloride particles, polyester resin particles, polyamide resin particles, polyolefin resin particles, and silicone resin particles.
In the present invention, the first and second scattering particles may be contained in a weight ratio of 30:70 to 70:30.
In the present invention, it may further comprise a catalyst selected from the group consisting of titanium oxide (TiO 2 ) Zinc oxide (ZnO), silicon oxide (SiO) 2 ) Barium sulfate (BaSO) 4 ) Zirconia (ZrO) 2 ) More than one kind of scattering particles in the group.
In the present invention, the photopolymerizable compound may include a compound represented by the following chemical formula 1.
[ chemical formula 1]
(in the above chemical formula 1, R 1 ～R 5 Each independently of the other can be a hydrogen atom, a methyl group or a hydroxyl group, R 6 Can be directly bonded or an alkylene group having 1 to 4 carbon atoms, and m can be an integer of 1 to 5. )
In the present invention, the photopolymerizable compound may further include a monofunctional monomer or a multifunctional monomer having 3 or more unsaturated double bonds.
In the present invention, the solvent may be contained in an amount of 10ppm to 9000ppm or not.
The present invention also relates to a light scattering laminated substrate produced using the light scattering ink composition.
The present invention also relates to a backlight unit including the light scattering laminated substrate.
The present invention also relates to a light-scattering pixel substrate produced using the light-scattering ink composition.
The present invention also relates to an image display device including the backlight unit or the light scattering pixel substrate.
Effects of the invention
The light scattering ink composition of the present invention has an effect of improving physical properties such as transmittance, haze (light scattering) properties, sedimentation stability, and adhesion by including the first scattering particles and the second scattering particles.
In addition, the light scattering ink composition exhibits excellent ejection characteristics and is suitable for application to an inkjet printing system, whereby manufacturing processes, time and costs can be significantly reduced.
Further, by applying the light scattering ink composition of the present invention, a light scattering laminated substrate, a light scattering pixel substrate, and an image display device excellent in reliability can be provided.
Detailed Description
The present invention relates to a light scattering ink composition containing first scattering particles as inorganic particles, second scattering particles as organic particles, a photopolymerizable compound, and a photopolymerization initiator. Specifically, the first scattering particles may have an average particle diameter of more than 100nm and less than 350nm, the second scattering particles may have an average particle diameter of more than 40nm and less than 400nm, and the first scattering particles may be selected from titanium oxide (TiO 2 ) Zinc oxide (ZnO), silicon oxide (SiO) 2 ) Barium sulfate (BaSO) 4 ) Zirconia (ZrO) 2 ) More than one kind of the group.
The present invention also relates to a light scattering laminated substrate, a light scattering pixel substrate, and an image display device manufactured using the light scattering ink composition.
Hereinafter, embodiments of the present invention will be described in more detail.
The inclusion and/or the presence of (having) as used in this specification is not intended to exclude the presence or addition of other elements, steps, acts, and/or components than those involved. Like reference numerals refer to like elements throughout the specification.
As used herein, "substantially" may be interpreted to include not only physically identical or consistent but also to include within an error range in a measurement or manufacturing process, for example, to be less than 0.1% of the error range.
< light-scattering ink composition >
The light scattering ink composition according to an embodiment of the present invention may further include one or more of the above-described first scattering particles, and may include a solvent or be solvent-free, as required, because the composition includes the first scattering particles, the second scattering particles, the photopolymerizable compound, and the photopolymerization initiator.
Scattering particles
The light scattering ink composition is characterized by comprising two or more scattering particles. The scattering particles may increase the path of light emitted from the light emitting particles by the scattering particles, thereby improving the overall light efficiency in the light conversion coating. The light scattering ink composition according to an embodiment of the present invention includes first scattering particles and second scattering particles, and specifically, the first scattering particles may be inorganic particles having an average particle size of more than 100nm and less than 350nm, and the second scattering particles may be organic particles having an average particle size of more than 40nm and less than 400 nm. By mixing the scattering particles different from each other, the transmittance of the coating film can be improved, the light scattering (haze) characteristics can be improved, and excellent ejection characteristics can be exhibited to be easily applied to the inkjet coating method. In addition, one or more types of the first scattering particles may be further contained as needed.
In the present invention, the first scattering particles include inorganic particles, and the second scattering particles include organic particles, so that the following advantages are obtained: the high refractive index of the inorganic particles can provide excellent light scattering properties, and the compatibility of the organic particles with the ink composition can be increased to improve particle aggregation or to improve adhesion and ejection properties. In addition, by setting the average particle diameters of the first scattering particles and the second scattering particles to a specific range, the sedimentation property can be controlled in addition to the above advantages.
The scattering particles may be added to the light scattering ink composition in the form of a dispersion, and may be produced by adding the first scattering particles, the second scattering particles, the dispersing agent, and/or the photopolymerizable compound to the dispersion, and mixing and dispersing the mixture. The above-mentioned dispersant may contain a dispersant commonly used in the art within a range not impairing the effect of the present invention, and examples thereof include DISPERBYK-2001 (Pick (BYK) Co.) and the like. The photopolymerizable compound can be used as described below, and therefore, a description thereof will be omitted.
First scattering particles
The first scattering particles preferably have an average particle diameter of more than 100nm and less than 350nm, more preferably 150nm to 300 nm. When the average particle diameter of the first scattering particles is within the above range, the particles can be uniformly distributed in the light scattering ink composition, and when the particle diameter is too large to be equal to or larger than the above range, the particles may be settled in the composition, and problems may occur in forming a uniform coating film. In addition, the effect of having high transmittance and light scattering characteristics can be obtained.
The first scattering particles are preferably inorganic particles, and the inorganic particles may be, for example, oxides containing one metal selected from the group consisting of Li, be, B, na, mg, al, si, K, ca, sc, V, cr, mn, fe, ni, cu, zn, ga, ge, rb, sr, Y, mo, cs, ba, la, hf, W, tl, pb, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, ti, sb, sn, zr, nb, ce, ta, in and combinations thereof. Still preferably, according to an embodiment of the present invention, the first scattering particles are preferably selected from the group consisting of titanium oxide (TiO 2 ) Zinc oxide (ZnO), silicon oxide (SiO) 2 ) Barium sulfate (BaSO) 4 ) Zirconia (ZrO) 2 ) More than one kind of the group.
Second scattering particles
The second scattering particles preferably have an average particle diameter of 40nm to 400nm, more preferably 50nm to 350 nm. When the average particle diameter of the second scattering particles is within the above range, the composition can exhibit a uniform distribution degree, and the effects of improving particle aggregation and adhesion and ejection properties can be obtained, as in the case of the first scattering particles.
The first scattering particles are preferably organic particles, and the organic particles are preferably at least one selected from the group consisting of polymethyl methacrylate particles, acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, acrylic-styrene copolymer particles, melamine particles, crosslinked melamine particles, benzoguanamine resin particles, polycarbonate particles, polyvinyl chloride particles, polyester resin particles, polyamide resin particles, polyolefin resin particles, and silicone resin particles.
The light scattering ink composition of the present invention may further contain one or more types of first scattering particles in addition to the first scattering particles and the second scattering particles. For example, when two or more types of first scattering particles are contained and the average particle diameters of the particles are different from each other, there is an advantage that the transmittance or the rate of change in light scattering characteristics can be adjusted according to the film thickness.
The content ratio of the first scattering particles to the second scattering particles is preferably 30:70 to 70:30, and may be included in a weight ratio of 40:60 to 60:40. When the first and second scattering particles satisfy the weight ratio range, the transmittance of the coating film can be improved, and the light scattering (haze) property can be improved. In particular, by controlling the sedimentation property, a light scattering ink composition having excellent ejection characteristics can be provided, and is therefore preferable.
The content of the scattering particles may be 1 to 50% by weight, preferably 3 to 45% by weight, and more preferably 3 to 40% by weight, based on 100% by weight of the total weight of the light scattering ink composition. In the case where the content of the scattering particles is within the above range, the light conversion efficiency can be improved. In the case of less than the above content range, light conversion efficiency is lowered and it may be difficult to realize a high-quality display device. If the content is more than the above-mentioned range, the component for realizing the curing is insufficient and the curing degree of the coating film is insufficient, whereby the productivity of the post-production process of the display device and the reliability of the product may be lowered.
Photopolymerizable compound
In the present invention, the photopolymerizable compound may include a compound represented by the following chemical formula 1.
[ chemical formula 1]
In the above chemical formula 1, R 1 ～R 5 Each independently of the other can be a hydrogen atom, a methyl group or a hydroxyl group, R 6 Can be directly bonded or an alkylene group having 1 to 4 carbon atoms, and m can be an integer of 1 to 5.
The compound represented by the above chemical formula 1 may include one selected from 1, 6-hexanediol diacrylate, dimethylene diacrylate, trimethylene diacrylate, tetramethylene diacrylate, pentamethylene diacrylate, hexamethylene diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, dibutylene glycol diacrylate, tributylene glycol diacrylate, tetramethylene glycol diacrylate, pentamethylene glycol diacrylate, dimethylene dimethacrylate, trimethylene dimethacrylate, tetramethylene dimethacrylate, pentamethylene dimethacrylate, hexamethylene dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, tributylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, pentamethylene glycol dimethacrylate, and glycerol dimethacrylate, but is not limited thereto.
In the case where the photopolymerizable compound contains the compound represented by the chemical formula 1, a light scattering ink composition excellent in jetting properties can be provided, and is therefore preferable.
The photopolymerizable compound of the present invention is a photopolymerizable compound which can be polymerized by the action of a photopolymerization initiator described later, and may further contain a monofunctional monomer, a difunctional monomer, a polyfunctional monomer, or the like, and preferably contains a monofunctional monomer or a polyfunctional monomer having 3 or more unsaturated double bonds.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
The type of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like.
In this case, when the ink composition further contains a polyfunctional curable monomer having three or more functions, the ink jet properties can be obtained when the viscosity of the ink composition is controlled to be within 80 cP.
The content of the photopolymerizable compound may be 10 to 95% by weight, and preferably 20 to 90% by weight, based on 100% by weight of the total weight of the light scattering ink composition. When the content of the photopolymerizable compound is within the above content range, there is an advantage that the light efficiency, the curing degree and the dispersion stability are improved and the strength and the smoothness of the pixel portion are good, as compared with the conventional photopolymerizable compound. When the content of the photopolymerizable compound is less than the above range, it is difficult to ensure fluidity for ink ejection, and when the content is more than the above range, the content of the scattering particles is insufficient and the problem of lowering the light efficiency may occur, so that the content is preferably within the above range.
Photopolymerization initiator
The photopolymerization initiator may be used without any particular limitation as long as it can polymerize the photopolymerizable compound. For example, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like, the photopolymerization initiator preferably uses one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, bisimidazole-based compounds, oxime-based compounds, thioxanthone-based compounds, and phosphine oxide compounds.
For example, when an oxime compound or a phosphine oxide compound is used for curing a thick film of 5 μm or more, more excellent physical properties can be ensured in terms of the curing density and surface roughness of the cured film.
Specific examples of the oxime-based compound include o-ethoxycarbonyl-. Alpha. -oxyimino-1-phenylpropane-1-one, and typical commercial products include Irgacure OXE 01 and OXE 02 from Basoff company.
As specific examples of the above phosphine oxide compound, darocur TPO, lucirin TPO, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, etc. of Basff company, as trimethylbenzoylphenyl phosphine oxide, are typical.
The content of the photopolymerization initiator may be 0.1 to 10 wt%, and preferably may be 0.5 to 8 wt%, based on 100 wt% of the total weight of the light-scattering ink composition. When the content of the photopolymerization initiator is within the above range, the light-scattering ink composition is preferably highly sensitive, the exposure time is shortened, and productivity can be improved. When the content of the photopolymerization initiator is less than the above range, sufficient hardness cannot be obtained due to insufficient curing by light, and when the content is greater than the above range, there is a problem that the photopolymerization initiator causes a rapid increase in the decrease in the light scattering efficiency of the scattering particles, and the desired luminous intensity cannot be obtained, so that there is an advantage that the intensity of the pixel portion and the smoothness of the surface of the pixel portion are improved when the composition is used in the above range.
The above photopolymerization initiator may further contain a photopolymerization initiator aid to improve the sensitivity of the light-scattering ink composition of the present invention. When the photopolymerization initiator is contained, there is an advantage that the sensitivity is further improved and the productivity is improved.
For example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organosulfur compounds having a thiol group can be preferably used as the photopolymerization initiator.
The photopolymerization initiator may be added as appropriate within a range that does not impair the effects of the present invention.
Solvent(s)
The light scattering ink composition according to an embodiment of the present invention may further contain a solvent, or may be a solvent-free type containing no solvent. In the case where the light scattering ink composition of the present invention contains a solvent, for example, the solvent may be further contained at a concentration of 10ppm to 9000ppm relative to the light scattering ink composition.
Preferably, the light scattering ink composition of an embodiment of the present invention may be a solvent-free type containing no solvent from the viewpoint of continuous process. Even if the light scattering ink composition of the present invention is a solvent-free type containing no solvent, the light scattering ink composition containing the polymerizable monomer is excellent in light characteristics and dispersibility of scattering particles, and can realize low viscosity and excellent in nozzle ejection characteristics of the ink.
Examples of the solvent include ether and ester solvents, aliphatic saturated hydrocarbon solvents, halogenated hydrocarbon solvents, and aromatic hydrocarbon solvents, and examples include Propylene Glycol Methyl Ether Acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetate such as methyl cellosolve acetate and ethyl cellosolve acetate, alkylene glycol alkyl ether acetate such as propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxyamyl acetate, ketones such as benzene, toluene, xylene, and mesitylene, alcohols such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like, cyclic esters such as 3-ethoxypropionate, and the like, and the gamma-butyrolactone and the like.
Additive agent
In order to improve the flatness or adhesion of the coating film, the light scattering ink composition of the present invention may further contain additives commonly used in the art, if necessary, in addition to the above-described components, within a range not departing from the object of the present invention. Examples of the additives include, but are not limited to, surfactants, antioxidants, and adhesion promoters.
The light scattering ink composition of the present invention may further contain a fluorine-based surfactant or a sorbitan-based surfactant as a surfactant in addition to the compound represented by the above chemical formula 1 to improve the flatness of the coating film. In the case of mixing two or more surfactants having particle sizes and structures different from each other, there is an advantage of being uniformly dispersed at the time of inkjet ejection, and it is more advantageous in that the effect of protecting the quantum dot surface from oxygen or moisture penetration in the process can be provided.
The light scattering ink composition of the present invention may further comprise a fluorine-based surfactant. For example, BM-1000, BM-1100 (BM Chemie Co.), fluorad FC-135/FC-170C/FC-430 (Sumitomo 3M Co.), SH-28PA/-190/-8400/SZ-6032 (Torile Silicone Co.), megaface F-554/Megaface F-559/Megaface F-563 (DIC Co.), and the like may be used as the fluorine-based surfactant.
When the content of the fluorine-based surfactant is 0.01 to 5 wt% based on 100 wt% of the total weight of the light-scattering ink composition, there is an advantage of excellent dispersibility.
The light scattering ink composition of the present invention may further contain a sorbitan-based surfactant instead of the above-mentioned fluorine-based surfactant. For example, one can use20、/>20 (sigma-Aldrich) company, etc., but is not limited thereto.
The content of the sorbitan-based surfactant may be 0.01 to 15 wt%, and preferably 0.5 to 10 wt%, based on 100 wt% of the total weight of the light-scattering ink composition. When the content is less than the above range, the dispersibility improving ability is lowered, and when it exceeds the above range, the formation of the dosage form is adversely affected.
In one embodiment, the light scattering ink composition of the present invention may contain an antioxidant. The antioxidant can prevent oxidation of the light scattering ink composition and a coating film formed therefrom, and further improve light scattering characteristics and color purity.
The antioxidant can prevent oxidation of the light scattering ink composition and a coating film formed therefrom, and further improve light scattering characteristics and color purity. The antioxidant is not particularly limited as long as it can further improve the light scattering property and color purity of the light scattering ink composition, and preferably contains one or more of antioxidants containing phenols and phosphorus or antioxidants containing phenols and sulfur, and there isGP (sumitomo chemical company) and the like, but is not limited thereto.
The adhesion promoter may be added to improve adhesion to the substrate, and may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof, but is not limited thereto.
Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane and the like can be used, but are not limited thereto.
In addition, the light scattering ink composition of the present invention may further contain an additive such as an ultraviolet absorber, an anticoagulant or a dispersant within a range not impairing the effect of the present invention, and the ultraviolet absorber, the anticoagulant or the dispersant may be added and used by those skilled in the art as appropriate within a range not impairing the effect of the present invention.
The additive may be used in an amount of 0.01 to 15 wt%, specifically 0.02 to 12 wt%, more specifically 0.10 to 10 wt%, based on 100 wt% of the total weight of the light scattering ink composition, but is not limited thereto. When the content of the additive is within the above range, the coating property, flatness, adhesion, and the like of the light scattering ink composition can be improved, which is preferable. When the content of the additive is less than the above range, the desired effect such as coating property, flatness, adhesion and the like may be insufficient, and when the content is more than the above range, there is a problem that the content of the scattering particles or the polymerizable monomer is reduced to decrease the light emission intensity, the curing degree of the cured film is decreased and the like, so that when the composition is used in the above range, there is an advantage that the strength of the pixel portion and the physical properties such as coating property, flatness, adhesion and ejection property of the surface of the pixel portion are improved.
< light-scattering layered substrate, light-scattering pixel substrate, and image display device >
An embodiment of the present invention is a light-scattering laminated substrate that absorbs light emitted from a light-emitting element and converts the light into blue, green, or red light for emission, and the light-scattering laminated substrate may be formed using the light-scattering ink composition.
The present invention also provides a light-scattering pixel substrate that exhibits RED (RED), GREEN (GREEN), and BLUE (BLUE) color filter functions, which is manufactured using the light-scattering ink composition. For example, in the present invention, the above-described "light scattering pixel substrate" may be mixed with "color filter".
The light-scattering laminated substrate and/or the light-scattering pixel substrate may be formed by applying the light-scattering ink composition to a predetermined region by an inkjet method, and then curing the applied light-scattering ink composition.
Examples of the base material include, but are not limited to, flat surface substrates such as glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, polyimide substrates, al substrates, gaAs substrates, and the like. These substrates may be subjected to pretreatment such as reagent treatment with a reagent such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, vapor phase reaction treatment, and vacuum vapor deposition treatment. In the case of using a silicon substrate or the like as a substrate, a Charge Coupled Device (CCD), a Thin Film Transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like. Alternatively, a matrix of barrier ribs may be formed. The above-mentioned curing may be performed in accordance with heat curing conditions.
For example, the curing may be carried out at 100 to 250℃and preferably 150 to 230℃for 5 to 60 minutes and preferably 10 to 60 minutes.
In order to form an appropriate phase (phase) on a substrate by ejecting from a piezoelectric inkjet head, which is an example of an inkjet ejector, characteristics such as viscosity, fluidity, quantum dot particles, and the like need to be matched to the inkjet head. The piezoelectric ink jet head used in the present invention is not limited, and ejects ink having a droplet size of about 3 to 100pL, preferably about 5 to 40 pL.
The viscosity of the light scattering ink composition of the present invention is suitably from about 3 to 50cP, more preferably adjusted in the range of 7 to 40 cP.
The light scattering laminated substrate of the present invention can exhibit excellent light output when applied to blue, green and/or red light sources.
An embodiment of the present invention relates to a backlight unit characterized by comprising a light scattering laminated substrate applied to the above-described blue, green, and/or red light sources.
The backlight unit may further include a light guide plate, a reflection plate, and the like, which are commonly included.
An embodiment of the present invention relates to an image display device including the backlight unit and/or the light scattering pixel substrate.
The image display device of the present invention includes not only a usual liquid crystal display device but also various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.
In the following, in order to facilitate understanding of the present invention, experimental examples including specific examples and comparative examples are provided, but this is merely to illustrate the present invention and not to limit the scope of the appended claims, and it is obvious to those skilled in the art that various changes and modifications may be made to the embodiments within the scope and technical spirit of the present invention, and that such changes and modifications also fall within the scope of the appended claims. In addition, "%" and "parts" representing contents are weight basis as follows unless otherwise stated.
Manufacturing example: manufacture of scattering particle dispersion
45 parts by weight of each scattering particle in table 1 below, 5 parts by weight of DISPERBYK-2001 (manufactured by pick corporation) as a dispersing agent, and 50 parts by weight of 1, 6-hexanediol diacrylate as a photopolymerizable compound were mixed and dispersed for 12 hours by a bead mill, to prepare each scattering particle dispersion. The average particle diameter in the dispersion was measured using ELSZ-2000ZS (manufactured by Osaka corporation).
TABLE 1
| First scattering particles | Species of type | Average particle diameter | Second scattering particles | Species of type | Average particle diameter |
| I1 | TiO 2 | 100nm | O1 | Acrylic particles | 150nm |
| I2 | TiO 2 | 150nm | O2 | Acrylic particles | 200nm |
| I3 | TiO 2 | 180nm | O3 | Acrylic particles | 400nm |
| I4 | TiO 2 | 220nm | O4 | Crosslinked acrylic acid series | 40nm |
| I5 | TiO 2 | 280nm | O5 | Crosslinked acrylic acid series | 70nm |
| I6 | TiO 2 | 350nm | O6 | Crosslinked acrylic acid series | 150nm |
| I7 | ZnO | 210nm | O7 | Crosslinked acrylic acid series | 450nm |
| I8 | ZnO | 250nm | O8 | Melamine system | 100nm |
| I9 | SiO 2 | 190nm | O9 | Melamine | 200nm |
| I10 | SiO 2 | 240nm | O10 | PMMA system | 50nm |
| I11 | BaSO4 | 225nm | O11 | PMMA system | 90nm |
| I12 | BaSO4 | 260nm | O12 | Polystyrene | 75nm |
| I13 | ZrO 2 | 170nm | O13 | Polystyrene | 200nm |
| I14 | ZrO 2 | 260nm | O14 | Polystyrene | 250nm |
Examples 1 to 20 and comparative examples 1 to 7: manufacture of light scattering ink compositions
Light scattering ink compositions (unit: wt%) were prepared by mixing the compositions and contents shown in tables 2 to 4 below.
TABLE 2
TABLE 3
TABLE 4
-photopolymerizable compound (B): 1, 6-hexanediol diacrylate (Sigma Aldrich Co.)
Photopolymerization initiator (C): 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (Sigma Aldrich Co.)
Experimental example
The light scattering ink compositions produced in the above examples and comparative examples were used and the physical properties were evaluated as follows.
(1) Light scattering coating manufacture, transmittance measurement and haze measurement
The light scattering ink compositions of examples and comparative examples were applied by inkjet method to 5cmX cm glass substrates, respectively, and then applied at 1000mJ/cm using a 395nm light source 2 After the irradiation, the light scattering coating was manufactured by heating in a heating oven at 180℃for 30 minutes.
For the produced light scattering coating, the transmittance was measured by QE-2100 (Osaka Co.) and the coating haze was measured by HM-150 (color technology institute on village (Murakami Color Research Laboratory)). The measured results were evaluated according to the following evaluation criteria, and are shown in table 5 below.
< transmittance evaluation criterion >
And (3) the following materials: the transmittance is more than 60 percent
O: the transmittance is more than 58% and less than 60%
Delta: the transmittance is more than 55% and less than 58%
And (c): the transmittance is less than 55%
< haze evaluation criterion >
And (3) the following materials: haze of more than 94%
O: haze of more than 92% and 94% or less
Delta: haze of more than 90% and 92% or less
And (c): haze of 90% or less
(2) Sedimentation stability confirmation
For the light scattering ink compositions manufactured in the above examples and comparative examples, sedimentation stability was evaluated using a stability analyzer (turbo lan LAB) apparatus. After placing 30g of the light scattering ink composition in a 40ml vial (visual) for a stability analyzer and standing at room temperature for 24 hours, the rate of change of back scattering (Backscattering) at the TOP (TOP) was confirmed, and the results are shown in table 5 below.
(3) Number of continuous injections
After filling the respective light scattering ink compositions of examples and comparative examples in the inkjet printing apparatus of Unijet corporation, the temperature of the ejection head was fixed at 40 ℃, and then the operation of discharging the ink for 1 minute and then leaving for 30 minutes was repeated until the discharge was stopped due to the clogging of the nozzle of the ejection head, whereby the number of continuous ejections was evaluated, and the results are shown in table 5 below.
(4) Particle aggregation inside and on the surface of a pixel
The pixel interior and surface portions of the light scattering coating manufactured as described above were measured by a Scanning Electron Microscope (SEM), and the degree of particle aggregation was evaluated with naked eyes, and is shown in table 5 below.
< evaluation criterion for particle aggregation >
And (3) the following materials: without particle aggregation
O: particle aggregation area in area is less than 5%
Delta: the particle aggregation area in the area is more than 5% and less than 10%
And (c): the particle aggregation area in the area is more than 10 percent
(5) Adhesion of
The light scattering coating thus produced was subjected to a cross cut test according to ASTM D3359, and the adhesion at this time was evaluated according to the following evaluation criteria, and is shown in table 5 below.
< evaluation criterion >
OB: breaking into slices and falling off by more than 65 percent
1B: the end of the cutting part and the lattice are separated and the area is more than 35% and less than 65%
2B: the small area of the crossing part of the cutting part is fallen off and the area is more than 15% and less than 35%
3B: the crossing portion of the cutting part has small area falling off and the area is more than 5% and less than 15%
4B: the crossing part of the cutting part has small area falling off and the area is less than 5%
5B: lattice with smooth end of cut portion and no falling off [ Table 5]
Referring to the experimental data in table 5, it was confirmed that the light scattering ink composition of the present invention exhibited excellent effects in terms of transmittance, haze characteristics, sedimentation stability, and adhesion, and also exhibited excellent results of evaluation of the number of continuous ejection times, aggregation of particles inside the pixel, and aggregation of surface particles, in particular, excellent ejectability. In particular, examples 18 to 20, which further include one or more types of first scattering particles as compared with examples 1 to 17, showed that the transmittance, haze characteristics, intra-pixel particle aggregation, and surface particle aggregation evaluation results were more excellent as a whole as compared with examples 1 to 17. Specifically, by further comprising one or more compounds having a refractive index lower than that of TiO 2 Can exhibit an additional transmittance improving effect. For reference, for examples 16 and 17 in which the content ratio of the first scattering particles to the second scattering particles was out of the range of 30:70 to 70:30, while showing excellent physical properties compared with comparative examples, the ejection properties showed inferior results to those of examples 1 to 15.
In contrast, in comparative examples 1 to 7 in which the average particle diameter of the first scattering particles and/or the second scattering particles was out of the range of the present invention, it was confirmed that the results were significantly lower than those of examples in terms of transmittance, haze characteristics, sedimentation stability, adhesion, and ejection characteristics on one or more evaluation criteria.
Claims (12)
1. A light scattering ink composition comprising first scattering particles, second scattering particles, a photopolymerizable compound, and a photopolymerization initiator,
the first scattering particles have an average particle size of greater than 100nm and less than 350nm,
the second scattering particles have an average particle size of greater than 40nm and less than 400nm,
the first scattering particles are selected from titanium oxide TiO 2 Zinc oxide ZnO, silicon oxide SiO 2 Barium sulfate BaSO 4 Zirconia ZrO 2 One or more of the group consisting of,
the second scattering particles are organic particles.
2. The light scattering ink composition according to claim 1,
the first scattering particles have an average particle diameter of 150nm to 300nm,
the second scattering particles have an average particle diameter of 50nm to 350 nm.
3. The light-scattering ink composition according to claim 1, wherein the organic particles are at least one selected from the group consisting of polymethyl methacrylate particles, acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, acrylic-styrene copolymer particles, melamine particles, crosslinked melamine particles, benzoguanamine resin particles, polycarbonate particles, polyvinyl chloride particles, polyester resin particles, polyamide resin particles, polyolefin resin particles, and silicone resin particles.
4. The light scattering ink composition of claim 1, the first and second scattering particles being included in a weight ratio of 30:70 to 70:30.
5. The light scattering ink composition of claim 1, further comprising a metal selected from the group consisting of titanium oxide TiO 2 Zinc oxide ZnO, silicon oxide SiO 2 Barium sulfate BaSO 4 Zirconia ZrO 2 More than one kind of scattering particles in the group.
6. The light scattering ink composition according to claim 1, wherein the photopolymerizable compound comprises a compound represented by the following chemical formula 1,
chemical formula 1
In the above-mentioned chemical formula 1,
R 1 ～R 5 each independently is a hydrogen atom, a methyl group or a hydroxyl group,
R 6 is a direct bond or an alkylene group having 1 to 4 carbon atoms,
m is an integer of 1 to 5.
7. The light scattering ink composition according to claim 6, wherein the photopolymerizable compound further comprises a monofunctional monomer or a polyfunctional monomer having 3 or more unsaturated double bonds.
8. The light scattering ink composition of claim 1, comprising 10ppm to 9000ppm of solvent or not comprising solvent.
9. A light scattering laminated substrate manufactured using the light scattering ink composition according to any one of claims 1 to 8.
10. A backlight unit comprising the light scattering laminated substrate of claim 9.
11. A light scattering pixel substrate manufactured using the light scattering ink composition according to any one of claims 1 to 8.
12. An image display device comprising the backlight unit of claim 10 or the light scattering pixel substrate of claim 11.
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