WO2014176915A1 - 黑色光阻组合物、其制备方法、彩色滤光片和显示器件 - Google Patents

黑色光阻组合物、其制备方法、彩色滤光片和显示器件 Download PDF

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WO2014176915A1
WO2014176915A1 PCT/CN2013/089879 CN2013089879W WO2014176915A1 WO 2014176915 A1 WO2014176915 A1 WO 2014176915A1 CN 2013089879 W CN2013089879 W CN 2013089879W WO 2014176915 A1 WO2014176915 A1 WO 2014176915A1
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Prior art keywords
infrared light
photoresist composition
black photoresist
emitting
composition capable
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PCT/CN2013/089879
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English (en)
French (fr)
Inventor
杨久霞
白峰
赵一鸣
孙晓
白冰
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京东方科技集团股份有限公司
北京京东方光电科技有限公司
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Application filed by 京东方科技集团股份有限公司, 北京京东方光电科技有限公司 filed Critical 京东方科技集团股份有限公司
Priority to US14/387,770 priority Critical patent/US9529256B2/en
Publication of WO2014176915A1 publication Critical patent/WO2014176915A1/zh

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix

Definitions

  • Black photoresist composition preparation method thereof, color filter and display device
  • Embodiments of the present invention relate to a black photoresist composition capable of emitting infrared light, a method of preparing the black photoresist composition capable of emitting infrared light, comprising a black matrix formed by the black photoresist composition capable of emitting infrared light a color filter, and a display device including the color filter. Background technique
  • the conventional color filter for black color resisting material includes a coloring agent for coloring, an ethylenically unsaturated monomer, an alkali-soluble resin, a solvent, a photoinitiator, an additive, and the like.
  • far infrared rays have strong penetrating power and radiation force, and have significant temperature control effects and resonance effects.
  • water molecules in the body can resonate, activate water molecules, and enhance their intermolecular binding force. , thereby activating biological macromolecules such as proteins, so that the living cells are at the highest vibrational level.
  • biological macromolecules such as proteins
  • Due to the resonance effect of biological cells the far-infrared heat energy can be transmitted to the deeper part of the human skin, and the deep temperature rises below, and the generated warm heat is emitted from the inside to the outside.
  • This action intensity expands the capillaries, promotes blood circulation, strengthens the metabolism between tissues, increases the regenerative capacity of the tissues, enhances the body's immunity, and regulates the abnormal state of excitement, thereby playing a role in medical care.
  • a black photoresist composition is developed on the basis of a conventional black photoresist material, which increases the function of emitting infrared rays, so that the display device produced therefrom has both the traditional display effect and the The efficacy of health care.
  • Embodiments of the present invention provide a black photoresist composition capable of emitting infrared light, which can generate a sufficient amount of infrared rays and maintain display performance such as conventional optical density value and chromaticity, and at the same time realizes health care and display.
  • a black photoresist composition capable of emitting infrared light, comprising the following components by weight based on the total weight of the composition: 2% to 15% of a color mixed material, 30% to 90% Solvent, 2% to 20% alkali-soluble resin, 2% to 20% ethylenically unsaturated monomer, 0.01% to 1% photoinitiator, and 0.005% to 0.02% other additives; wherein, the coloring
  • the mixed material includes a colorant and a surface-modified infrared light-emitting material in a weight ratio of 19:1 to 1:1.
  • the colored mixed material comprises a colorant and a surface-modified infrared light-emitting material in a weight ratio of 6:1 to 1:1.
  • the infrared light emitting material is one or more selected from the group consisting of tourmaline, biochar, far infrared ceramic, jade powder, aluminum oxide, copper oxide, silver oxide, and silicon carbide.
  • the infrared light emitting material is modified by the surface of the polymeric material.
  • the polymeric material is a copolymer of decyl acrylate-styrene-maleimide.
  • the surface-modified infrared light-emitting material has an average particle diameter of from 1 nm to 200 nm.
  • the tourmaline is black tourmaline, and has a density of 3.06 to 3.26 g/cm 3 and a refractive index of 1.62 to 1.64.
  • a black photoresist composition capable of emitting infrared light, comprising the steps of:
  • the infrared light emitting material is ground and dispersed in a solvent to obtain a nano-dispersed solution containing infrared light-emitting material nanoparticles having an average particle diameter of 1 nm to 200 nm; surface modification, followed by solvent removal to obtain infrared modified by the polymer material Light emitting material nanoparticles; to coloring the mixed material, and
  • the colored mixed material is mixed with a solvent, an alkali-soluble resin, an ethylenically unsaturated monomer, a photoinitiator, and other additives to obtain a black photoresist composition capable of emitting infrared light.
  • a color filter comprising a black matrix formed of the above-described black photoresist composition capable of emitting infrared light.
  • a display device including the above color filter is provided.
  • the display device produced by the black photoresist composition capable of emitting infrared light can generate a sufficient amount of infrared rays while maintaining the display performance such as the original optical density (OD) value, thereby achieving both health care and display.
  • Embodiments of the present invention provide a black photoresist composition capable of emitting infrared light, comprising: 2% to 15% of a colored mixed material, 30% - 90% of a solvent based on the total weight of the composition 2% ⁇ 20% alkali-soluble resin, 2% ⁇ 20% ethylenically unsaturated monomer, 0.01% ⁇ 1% photoinitiator and 0.005% ⁇ 0.02% other additives.
  • the coloring mixed material is contained in an amount of 2 to 15%, preferably 5% to 15%, more preferably 5% to 10% based on the total mass of the composition.
  • the coloring mixed material comprises a weight ratio of 19:1 to 1 :1, preferably 11:3 to 1:1, more preferably 9:5 to 1 : 1 colorant and surface modified infrared light emitting material.
  • the above colorant may be a black pigment, a black dye, or a mixture of two or more thereof.
  • Examples of the above black pigment may include a carbon black pigment and an organic black pigment.
  • the carbon black pigment may be, for example, Printex IA Printex L Printex 55, Printex 45, Printex 60, Te Black 550, Te Black 350, Printex 35, réelle 250, Printex 25, réelle 100, Printex 200 from DEGUSSA.
  • the organic black pigment may be, for example, L0080 and L0086 from BASF; and CCA1 and CCA2 from Central Synthetic Chemistry of Japan.
  • Examples of the above black dye may include C.I. Direct Blackl9 C.I. Direct Black22 C.I. Direct Blackl 54 C ⁇ Direct Blackl68, Dye 11, Dyes 12, Dyes 13, Dyes 14 Dyes 15, Dyes 16, Dyes 17, Dyes 18 and the like.
  • the above-mentioned infrared light-emitting material is a material capable of generating infrared light by heat exchange, and examples thereof may include a material selected from tourmaline ([Na, K, Ca] [Mg, F, Mn, Li, Al] 3 [Al, Cr, Fe ,V] 6 [B0 3 ] 3 [Si 6 0 18 ][OH,F]4> one or more of biochar, far infrared ceramic, jade powder, aluminum oxide, copper oxide, silver oxide and silicon carbide
  • the average particle diameter is from 1 nm to 200, preferably from 5 nm to 150 nm, more preferably from 10 nm to 100 nm, and most preferably from 25 nm to 75 nm.
  • the infrared light emitting material is preferably tourmaline, biochar, alumina or silicon carbide.
  • the tourmaline is preferably black tourmaline, and its hardness is 7 ⁇ 7.2, the density is 3.06 ⁇ 3.26g / cm 3 , and the refractive index is 1.62 ⁇ 1.64.
  • the biochar preferably has a specific surface area of 550 to 750 m 2 /g, and a density of 1.3 to 1.5 g/cm 3 .
  • the above-mentioned infrared light-emitting material cannot be used in the embodiment of the present invention without surface treatment because it is incompatible with the organic resin and the pigment component in the black photoresist composition system, and is liable to cause precipitation and separation of the photoresist composition.
  • the phase causes the performance of the photoresist material to deteriorate, affecting the uniformity of the display effect.
  • the surface modification treatment of the above-mentioned infrared light emission treatment is performed before use, in order to change the surface morphology and the grain boundary structure, thereby changing the activity of the material, improving the heat exchange capacity, and enabling it to emit a specific wavelength at a high specific emissivity. Far infrared rays.
  • the surface modification process for the infrared light emitting material may include:
  • the grinding and dispersing method can be carried out by a usual method for preparing a nano material, for example, by using a conventional grinding apparatus (e.g., a ball mill, a sand mill, etc.) and a dispersing agent in an organic solvent.
  • a conventional grinding apparatus e.g., a ball mill, a sand mill, etc.
  • the weight percentage of the infrared light-emitting material in the nano-dispersion solution may be 10 ⁇ based on the total weight of the nano-dispersion solution.
  • 2) further surface modification of the nano-treated infrared light-emitting material, the purpose of this step is to change the surface characteristics of the dispersed nanoparticles in step 1) to make them compatible with the black photoresist composition system. Specifically include:
  • An azo initiator such as azobisisovaleronitrile, azobisisobutyronitrile, azobisisohexonitrile, azobisisoheptanenitrile or the like is dissolved in an organic solvent for use;
  • the nano-dispersion of the infrared light-emitting material is dissolved into a four-necked bottle, and simultaneously stirred, oscillated (frequency is higher than 50 Hz) or shaken;
  • a solution of a monomeric decyl decyl acrylate, styrene, maleimide (l:1 ⁇ 2:1 ⁇ 2 / mol) in an organic solvent (monomer: solvent 1:1 ⁇ 3 / vol) Adding to the above four-necked bottle, wherein the infrared light-emitting material accounts for 8 to 25%, preferably 10 to 20%, more preferably 12 to 17%, of the total weight of the mixed solution in the four-necked bottle; at 35 ° C to 60 ° C, In a nitrogen atmosphere, the azo initiator solution is added dropwise to the above four bottles in an amount of from 1 to 5% based on the total weight of the monomers, and the reaction is carried out under stirring, shaking or shaking for 30 min. 90min;
  • the filtered solid was washed three times with the above organic solvent, and dried at 70 to 100 ° C for 5 to 20 minutes to obtain a surface-modified infrared light-emitting material.
  • the solvent used in the above steps may be fatty alcohol, glycol ether, ethyl acetate, ethyl ketone, decyl isobutyl ketone, monodecyl ether ethylene glycol ester, ⁇ -butyrolactone, propionic acid-3- One or more of diethyl ether, butyl carbitol, butyl carbitol acetate, propylene glycol monodecyl ether, propylene glycol monodecyl ether acetate, cyclohexane, diphenylbenzene, isopropanol .
  • the dispersing agent used in the above steps is a usual dispersing agent such as ⁇ 410, ⁇ 110, ⁇ 163, BYK 161, BYK 2000, CN2284, Solsperse 32500, Solsperse 22000 and the like.
  • the dispersant accounts for 5% to 15% by weight of the nanodispersion solution, preferably 7 to 12%.
  • the weight percentage of the solvent may be 30% to 90%, preferably 40% to 90%, more preferably 45% to 90%, based on the total weight of the composition. %.
  • the solvent may be one or more of an acidic solvent, an alkaline solvent, and a neutral solvent. Acidic Examples of the solvent may include formic acid, acetic acid or chloroform and the like. Examples of the alkaline solvent may include some basic ketones, esters, ethers or certain aromatic hydrocarbon solvents and the like.
  • Examples of the neutral solvent may include fatty alcohols, glycol ethers, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, monomethyl ether glycol ester, ⁇ -butyrolactone, propionic acid-3-ethyl ether Ester, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, xylene, isopropanol and the like.
  • Preferred is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, butyl carbitol, butyl carbitol acetate or ⁇ -butyrolactone, or a mixture thereof.
  • the alkali-soluble resin content is 2 wt% to 20 wt%, preferably 5 wt% to 20 wt%, more preferably 5 wt%, based on the total weight of the composition. % ⁇ 15 wt %.
  • the alkali-soluble resin may be an aromatic acid (meth) acrylate half ester (e.g., SB401, SB404 from Sartomer), a styrene and maleic anhydride copolymer, or a combination of two or more.
  • the monomer may be an ethylenically unsaturated monomer, and the content thereof is 2 wt% to 20 wt%, preferably 5 wt%, based on the total weight of the composition. % ⁇ 20 wt%, more preferably 5 wt% ⁇ 15 wt%.
  • the ethylenically unsaturated monomer may be vinyl chloride, styrene, methyl methacrylate, maleimide, butadiene, methyl acrylate, epoxy acrylate, bisphenol A epoxy methyl acrylate, and more A functional (meth) acrylate monomer (for example, ethoxylated trimethoxypropane triacrylate, pentaerythritol tetraacrylate, or the like), or a combination of two or more of the above.
  • a functional (meth) acrylate monomer for example, ethoxylated trimethoxypropane triacrylate, pentaerythritol tetraacrylate, or the like
  • the photoinitiator content is 0.01 wt% to 1 wt% based on the total weight of the composition, wherein the photoinitiator may be an ⁇ -amino ketone.
  • Photoinitiator such as Irgacure 907, Igracure 369, Irgacure 1300; or acylphosphine oxide photoinitiator, Irgacure 819, Irgacure 819DW, Irgacure 2010, Darocur TPO, Darocur 4265; may be alpha-hydroxyketone photoinitiator , such as Darocur 1173, Irgacure 184, Irgacure 2959, Irgacure 500, Irgacure 1000; or benzoic acid photoinitiator, such as Darocur MBF, Irgacure 754; may be oxyacyl oxime ester photoinitiators, such as OXE-01, OXE -02, Quanta cure PDO; One or a mixture of two or more of the above may be used.
  • the other additive content is 0.005 wt% - 0.02 wt%, preferably 0.005 wt% ⁇ 0.015, based on the total weight of the composition. Wt%, more preferably 0.005 wt% ⁇ 0.01 wt%.
  • the additive may be an adhesion promoter, a leveling agent, an antifoaming agent, a light stabilizer, or the like.
  • the colorant is mixed with the surface-modified infrared light-emitting material in a weight ratio of 19:1 to 1:1 to obtain a colored mixed material.
  • the above colored mixed material, solvent, alkali-soluble resin, ethylenically unsaturated monomer, photoinitiator and other additives are uniformly mixed at the above content, for example, by stirring, shaking, or the like, thereby preparing the infrared light capable of emitting infrared light of the present invention.
  • Photoresist composition Therefore, the black photoresist composition having the above composition can emit far-infrared light in the range of 5 to 15 ⁇ m, and the specific emissivity is 0.35 to 0.95, while maintaining the display performance such as conventional chromaticity and transmittance. Thereby having a health care effect.
  • B-1 Black tourmaline: Density 3.06g/cm 3 , refractive index 1.62, hardness 7
  • E-l EBE 350 (Cytec Chemical)
  • initiator F- 1 Irgacure 369 (Ciba Refined)
  • G-2 Leveling agent BYK 333
  • the above reaction product was filtered, and the filtered solid was washed three times with 50 mL of PMA, and dried at 90 ° C for 15 min to obtain an yttrium methacrylate-styrene-maleimide copolymer-modified alumina particle.
  • the average particle size was 24 nm.
  • the black pigment RAVEN 760 ULTRA was mixed with the above-described modified alumina particles in a weight ratio of 19:1 to obtain a colored mixed material-1.
  • the colored mixed material -2 to the colored mixed material -10 was prepared in the same manner as in Example 1, except that the mixing of the black pigment with the modified infrared light-emitting material was as shown in Table 1.
  • a dispersant solution was prepared by mixing 8 g of Solsperse 22000, 75 g of Solsperse 32500 and 40 g of CN 2284 with 423.5 g of solvent PMA by stirring. To the solution, 100 g of the colored mixed material -1 obtained in Example 1 was added, and the pigment was sufficiently wetted by stirring to obtain a mixed solution. The mixed solution was ground and dispersed by a sand mill to obtain a colored mixed material: liquid -1 in which the percentage of the colored mixed material was 15.5%.
  • Alkali-soluble resin D-1 (10%), D-2 (2%), ethylenically unsaturated monomer E-1 (10%), E-2 (3.8%), photoinitiator F-1 (0.007 %), F-2 (0.008%) and other additives G-1 (0.002%) and G-2 (0.013%) are added to the solvent C-2 (30%) and C-3 (10%) in a mixed solvent. Stir until completely dissolved to obtain a photocured solution.
  • the colored mixed material dispersion-1 prepared above is added to the photocuring solution, ground and mixed by a sand mill, and the solvent C-1 is replenished during the grinding so that the percentage of the colored mixed material in the black photoresist composition is 15%, and The percentage of the solvent C-1 was 19.17%, whereby a black photoresist composition-1 was obtained.
  • a black photoresist composition -2 to black resist composition -10 was prepared in the same manner as in Example 3 except that the composition ratio as shown in Table 1 was employed.
  • the black photoresist compositions-1 to 10 obtained in Examples 3 to 12 were coated on a glass substrate by spin coating. After the substrate coated with the black photoresist composition was baked at 90 ° C for 7 minutes, the black resist composition was exposed to ultraviolet light having an illuminance of 180 mJ/cm 2 for an exposure time of 15 seconds. After the exposed glass substrate was developed in an alkaline developing solution, it was baked at a temperature of 200 ° C for 20 minutes to form black matrix patterns 1 to 10 having a thickness of 1.5 ⁇ m.
  • Example 12 when the ratio of the colorant to the infrared light-emitting material is more than 6, the infrared ratio is higher than the radiance, as in Example 3 and Example 4. With respect to Example 12, since the content of the coloring material was low, the content of the colorant therein was low, resulting in a low optical density (small OD value) of the black photoresist material.
  • the infrared specific radiance of the photoresist composition is also low, and the photoresist composition increases as the content of the infrared light-emitting material in the colored mixed material increases.
  • the infrared specific radiance increases, but neither has a significant effect on the optical density of the photoresist.
  • BYK 161 5 g was added to 95 g of solvent propylene glycol monodecyl ether acetate (PMA) to which 11.lg of alumina particles were added. After the mixture was uniformly stirred, it was ground and pulverized in a sand mill to an average particle diameter of alumina of 17 nm to obtain an alumina nano-dispersion solution. The solvent in the aluminum oxide nano-dispersion solution is removed to obtain alumina nanoparticles.
  • PMA solvent propylene glycol monodecyl ether acetate
  • the black pigment RAVEN 760 ULTRA was mixed with the above alumina nanoparticles in a weight ratio of 19:1 to obtain a colored mixed material.
  • a comparative black photoresist composition was prepared in accordance with the procedure of Example 3.
  • Example 3 The two black photoresist compositions prepared in Example 3 and Comparative Example 1 were placed in a dark environment of 0 to 4 ° C to observe the delamination and precipitation of the photoresist composition.
  • Comparative black photoresist composition After 24 hours, the surface appeared crust and a small amount of precipitate was formed at the bottom of the container; after 48 hours, a large amount of agglomeration occurred during stirring, and solid particles agglomerated severely.
  • Black photoresist composition -1 No surface crust or bottom sedimentation was observed up to 48 hours, and agglomeration and agglomeration did not occur after stirring.
  • the black light-emitting composition capable of emitting infrared light can emit far-infrared rays having a health effect by adding nanoparticles that have undergone surface-modified infrared light-emitting materials while maintaining a conventional display. performance.

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Abstract

一种能发射红外光的黑色光阻组合物，制备该能发射红外光的黑色光阻组合物的方法，包括由该能发射红外光的黑色光阻组合物形成的黑色矩阵的彩色滤光片以及包括该彩色滤光片的显示器件。所述能发射红外光的黑色光阻组合物包括基于所述组合物总重的如下重量百分比的组分：2-15%的着色混合材料，30-90%的溶剂，2-20%的碱可溶性树脂，2-20%的乙烯性不饱和单体，0.01-1%的光引发剂和0.005-0.02%的其他添加剂；其中所述着色混合材料包括重量比为19:1-1:1的着色剂和表面改性的红外光发射材料。

Description

黑色光阻组合物、 其制备方法、 彩色滤光片和显示器件 技术领域
本发明实施例涉及一种能发射红外光的黑色光阻组合物， 制备该能发射 红外光的黑色光阻组合物的方法， 包括由该能发射红外光的黑色光阻组合物 形成的黑色矩阵的彩色滤光片， 以及包括该彩色滤光片的显示器件。 背景技术
随着显示技术的快速发展， 人们不仅要求显示器件能实现清晰、 仿真的 显示效果， 同时还对显示器件的功能多元化有了进一步要求， 例如显示器件 的娱乐性和保健性。
传统的显示器件借助于常规的彩色滤光片来实现彩色显示。 常规的彩色 滤光片用黑色光阻材料包括用于着色的着色剂、 乙烯性不饱和单体、 碱可溶 性树脂、 溶剂、 光引发剂、 添加剂等成分。
众所周知的， 远红外线有较强的渗透力和辐射力， 具有显著的温控效应 和共振效应， 被人体吸收后， 可使体内水分子产生共振， 使水分子活化， 增 强其分子间的结合力， 从而活化蛋白质等生物大分子， 使生物体细胞处于最 高振动能级。 由于生物细胞产生共振效应， 可将远红外热能传递到人体皮下 较深的部分， 以下深层温度上升， 产生的温热由内向外散发。 这种作用强度， 使毛细血管扩张， 促进血液循环， 强化各组织之间的新陈代谢， 增加组织的 再生能力， 提高机体的免疫能力， 调节精神的异常兴奋状态， 从而起到医疗 保健的作用。
基于以上需求和技术背景， 在常规的黑色光阻材料的基础上开发一种黑 色光阻组合物， 增加了发射红外线的功能， 使得由其制得的显示器件既具有 传统的显示效果， 又具有医疗保健的功效。 发明内容
本发明实施例提供了一种能发射红外光的黑色光阻组合物， 其既能产生 足够量的红外线， 又能保持常规的光密度值、 色度等显示性能， 同时实现了 保健与显示。
根据本发明的一个方面， 提供一种能发射红外光的黑色光阻组合物， 包 括基于组合物总重的如下重量百分比的组分： 2% ~ 15%的着色混合材料、 30% ~ 90%的溶剂、 2% ~ 20%的碱可溶性树脂、 2% ~ 20%的乙烯性不饱和单 体、 0.01% ~ 1%的光引发剂和 0.005% ~ 0.02%的其它添加剂； 其中， 所述着 色混合材料包括重量比为 19: 1 ~ 1 : 1的着色剂和表面改性的红外光发射材料。
根据本发明的一个实施方式， 所述着色混合材料包括重量比为 6: 1 ~ 1: 1 的着色剂和表面改性的红外光发射材料。
根据本发明的一个实施方式， 所述红外光发射材料为选自电气石、 生物 炭、 远红外陶瓷、 玉石粉、 氧化铝、 氧化铜、 氧化银以及碳化硅中的一种或 多种。
根据本发明的另一实施方式， 所述红外光发射材料经聚合物材料表面改 性。
所述聚合物材料为曱基丙烯酸曱酯 -苯乙烯-马来酰亚胺的共聚物。
所述表面改性的红外光发射材料具有 lnm ~ 200nm的平均粒径。
根据本发明的又一实施方式， 所述电气石为黑色电气石， 且密度为 3.06 ~ 3.26g/cm3, 折光率为 1.62 ~ 1.64。
根据本发明的另一个方面， 提供一种制备能发射红外光的黑色光阻组合 物的方法， 包括如下步骤：
将红外光发射材料研磨并分散于溶剂中， 得到包含平均粒径为 lnm ~ 200nm的红外光发射材料纳米粒子的纳米分散溶液； 面改性， 随后去除溶剂，得到经聚合物材料改性的红外光发射材料纳米粒子； 到着色混合材料， 并且 将所述着色混合材料与溶剂、 碱可溶性树脂、 乙烯性不饱和单体、 光引 发剂和其他添加剂混合， 得到能发射红外光的黑色光阻组合物。
根据本发明的又一个方面， 提供一种彩色滤光片， 包括由上述能发射红 外光的黑色光阻组合物形成的黑色矩阵。
根据本发明的又一个方面， 提供一种显示器件， 包括上述彩色滤光片。 由所述能发射红外光的黑色光阻组合物制得的显示器件既能产生足够量 的红外线， 又能保持原来的光密度 (OD)值等显示性能， 从而同时实现保健与 显示。 具体实施方式
本发明的实施例提供了一种能发射红外光的黑色光阻组合物， 包括基于 组合物总重的如下重量百分比的组分 2% ~ 15%的着色混合材料、 30% - 90% 的溶剂、 2% ~ 20%的碱可溶性树脂、 2% ~ 20%的乙烯性不饱和单体、 0.01% ~ 1%的光引发剂和 0.005% ~ 0.02%的其它添加剂。
在本发明实施例的能发射红外线的黑色光阻组合物中， 着色混合材料含 量为组合物总重的 2 ~ 15%, 优选 5% ~ 15%, 更优选 5% ~ 10%。
在本发明实施例的能发射红外光的黑色光阻组合物中， 上述着色混合材 料包括重量比为 19: 1 ~ 1 :1 , 优选 11:3 ~ 1: 1 , 更优选 9:5 ~ 1: 1的着色剂和表 面改性的红外光发射材料。
上述着色剂可为黑色颜料、 黑色染料， 或其两种或更多种的混合物。 上述黑色颜料的实例可包括炭黑颜料和有机黑颜料。 炭黑颜料例如可为 来自德固赛 (DEGUSSA)的 Printex IA Printex L Printex55、 Printex 45、 Printex 60、 特黑 550、 特黑 350、 Printex 35、 特黑 250、 Printex 25、 特黑 100、 Printex 200、 Hiblack 30, Hiblack 30L, 来自哥伦比亚的 Raven 1255、 Raven 1200、 Raven 1170、 Raven 1100 Ultra, Raven 1060 Ultra, Raven 1040、 Raven 1035、 Raven 102a Raven 1000、 Raven 890、 Raven 860 Ultra Raven 85( Raven 820、 Raven 760 Ultra, Raven 460、 Raven 450、 Raven 410、 Raven H20、 Raven 825 OB、 Raven 680 OB, 来自 CABOT的 R99R、 R250R、 R330R、 R400R、 R660R、 ML DL430等。
有机黑颜料例如可为来自 BASF的 L0080和 L0086; 以及来自日本中央 合成化学的 CCA1和 CCA2
上述黑色染料的实例可包括 C.I. Direct Blackl9 C.I. Direct Black22 C.I. Direct Blackl 54 C丄 Direct Blackl68、 染料 11、 染料 12、 染料 13、 染料 14 染料 15、 染料 16、 染料 17、 染料 18等。
上述红外光发射材料为能通过热交换产生红外光的材料， 其实例可包括 选自电气石（[Na,K,Ca][Mg,F,Mn,Li,Al]3[Al,Cr,Fe,V]6[B03]3[Si6018][OH,F]4>生 物炭、 远红外陶瓷、 玉石粉、 氧化铝、 氧化铜、 氧化银以及碳化硅中的一种 或多种； 其平均粒径为 lnm ~ 200 优选 5nm ~ 150nm, 更优选 lOnm - lOOnm, 最优选 25nm ~ 75nm
所述红外光发射材料优选为电气石、 生物炭、 氧化铝或碳化硅。 其中， 电气石优选黑色电气石， 且其硬度为 7 ~ 7.2, 密度为 3.06 ~ 3.26g/cm3, 折光 率为 1.62 ~ 1.64。 生物炭优选具有 550 - 750 m2/g的比表面积， 和 1.3 ~ 1.5 g/cm3的密度。
上述红外光发射材料未经表面处理不能用于本发明的实施方式中， 因为 其与黑色光阻组合物体系中的有机树脂及颜料组分的不相容， 易导致光阻组 合物沉淀及分相， 从而造成光阻材料的性能恶化， 影响显示效果的均匀性。 在使用前对上述红外光发射处理进行表面改性处理， 目的是改变其表面形 态、 晶界结构， 从而改变材料的活性， 提高其热交换能力， 能够使其以高的 比辐射率放射特定波长的远红外线。
对红外光发射材料的表面改性过程可包括：
1)将红外光发射材料研磨并分散于溶剂中， 获得包含平均粒径为 lnm ~ 200nm的红外光发射材料纳米粒子的纳米分散溶液， 该步骤的主要目的是对 红外光发射材料进行纳米化处理， 以获得红外光发射材料的纳米粒子。 该研 磨、 分散方法可用制备纳米材料的常用方法进行， 例如可采用常规的研磨装 置 (例如球磨机、 砂磨机等)和分散剂在有机溶剂中进行。 基于所述纳米分散 溶液的总重， 该纳米分散溶液中的红外光发射材料的重量百分比可为 10 ~ 2)将经过纳米化处理的红外光发射材料进行进一步的表面改性， 该步骤 的目的是改变步骤 1)中分散后的纳米粒子的表面特性， 使其与黑色光阻组合 物体系相容， 具体包括：
将诸如偶氮二异戊腈、 偶氮二异丁腈、 偶氮二异己腈、 偶氮二异庚腈等 的偶氮类引发剂溶解在有机溶剂中待用；
将红外光发射材料的纳米分散溶:^入四口瓶内， 同时对其进行搅拌、 震荡 (频率高于 50Hz)或摇动等处理；
将单体曱基丙烯酸曱酯、 苯乙烯、 马来酰亚胺 (l:l ~ 2:l ~ 2/mol)在有机溶 剂（单体：溶剂 =1:1 ~ 3/vol)中的溶液加入上述四口瓶内， 其中红外光发射材料 占四口瓶内混合溶液总重量的 8 ~ 25%, 优选 10 ~ 20%, 更优选 12 ~ 17%; 在 35°C ~ 60°C下、 氮气保护气氛中， 使偶氮类引发剂溶液以基于单体总 重量的 1 ~ 5%的引发剂的量逐滴加入上述四口瓶内， 在搅拌、 震荡或摇动等 处理下进行反应 30min ~ 90min;
反应结束后加入 5 ~ 10°C的有机溶剂进行冷却处¾ 同时搅拌直至反应产 物冷却至室温；
过滤后， 用上述有机溶剂清洗滤出的固体三次， 在 70 ~ 100°C下干燥 5 ~ 20min, 得到表面改性的红外光发射材料。
以上步骤中所用溶剂可为脂肪醇、 乙二醇醚、 乙酸乙酯、 曱乙酮、 曱基 异丁基酮、 单曱基醚乙二醇酯、 γ-丁内酯、 丙酸 -3-乙醚乙酯、 丁基卡必醇、 丁基卡必醇醋酸酯、 丙二醇单曱基醚、 丙二醇单曱基醚醋酸酯、 环己烷、 二 曱苯、 异丙醇中的一种或多种。
以上步骤中所用分散剂为常用分散剂， 例如 ΒΥΚ 410、 ΒΥΚ 110、 ΒΥΚ 163、 BYK 161、 BYK 2000、 CN2284、 Solsperse32500、 Solsperse22000等。 分散剂占纳米分散溶液的重量百分比为 5% ~ 15%, 优选为 7 ~ 12%。
在根据本发明实施例的能发射红外光的黑色光阻组合物中， 基于组合物 总重， 溶剂的重量百分比可为 30% ~ 90%, 优选 40% ~ 90%, 更优选 45% ~ 90%。 该溶剂可以为酸性溶剂、 碱性溶剂、 中性溶剂中的一种或多种。 酸性 溶剂的实例可包括甲酸、 乙酸或氯仿等。 碱性溶剂的实例可包括一些碱性的 酮、 酯、 醚或某些芳香烃溶剂等。 中性溶剂的实例可包括脂肪醇、 乙二醇醚、 乙酸乙酯、 甲乙酮、 甲基异丁基酮、 单甲基醚乙二醇酯、 γ-丁内酯、 丙酸 -3- 乙醚乙酯、 丁基卡必醇、 丁基卡必醇醋酸酯、 丙二醇单甲基醚、 丙二醇单甲 基醚醋酸酯、 环己烷、 二甲苯、 异丙醇等。 优选为丙二醇单甲基醚、 丙二醇 单甲基醚醋酸酯、 环己烷、 丁基卡必醇、 丁基卡必醇醋酸酯或 γ-丁内酯， 或 它们的混合物。
在根据本发明实施例的能发射红外光的黑色光阻组合物中， 基于组合物 总重， 碱可溶性树脂含量为 2 wt % ~ 20wt %, 优选 5 wt % ~ 20 wt %, 更优 选 5 wt% ~ 15 wt %。 该碱可溶性树脂可为芳香酸（甲基）丙烯酸半酯（例如， 得自沙多玛的 SB401、 SB404 )、 苯乙烯与马来酸酐共聚物， 或两种以上的组 合。
在根据本发明实施例的能发射红外光的黑色光阻组合物中， 单体可为乙 烯性不饱和单体， 基于组合物总重， 其含量为 2 wt% ~ 20 wt%, 优选 5 wt% ~ 20 wt%, 更优选 5 wt% ~ 15 wt%。 乙烯性不饱和单体可以是氯乙烯、 苯乙 烯、 甲基丙烯酸甲酯、 马来酰亚胺、 丁二烯、 丙烯酸甲酯、 环氧丙烯酸酯、 双酚 A型环氧丙烯酸甲酯， 多官能度 (甲基)丙烯酸酯单体 (例如乙氧基化三甲 氧基丙烷三丙烯酸酯、 季戊四醇四丙烯酸酯等)， 或上述两种以上的组合。
在根据本发明实施例的能发射红外光的黑色光阻组合物中， 基于组合物 总重， 光引发剂含量为 0.01 wt% - 1 wt%, 其中光引发剂可以是 α-胺基酮类 光引发剂， 如 Irgacure 907, Igracure 369, Irgacure 1300; 或酰基膦氧化物光 引发剂, ^口 Irgacure 819, Irgacure 819DW, Irgacure 2010, Darocur TPO, Darocur 4265; 可以是 α-羟基酮类光引发剂， 如 Darocur 1173, Irgacure 184 , Irgacure 2959, Irgacure 500, Irgacure 1000;或苯酰甲酸类光引发剂， 如 Darocur MBF, Irgacure 754;可以是氧酰基肟酯类光引发剂，如 OXE-01 , OXE-02, Quanta cure PDO; 可以使用上述一种或两种以上的混合。
在根据本发明实施例的能发射红外光的黑色光阻组合物中， 基于组合物 总重， 其它添加剂含量为 0.005 wt% - 0.02 wt%, 优选 0.005 wt% ~ 0.015 wt%, 更优选 0.005 wt% ~ 0.01 wt%。 其中添加剂可以为附着力促进剂、 流平 剂， 消泡剂、 光稳定剂等。
将着色剂与经表面改性的红外光发射材料以 19:1 ~ 1:1 的重量比混合得 到着色混合材料。
将上述着色混合材料、 溶剂、 碱可溶性树脂、 乙烯性不饱和单体、 光引 发剂和其它添加剂以上述含量均匀混合， 例如通过搅拌、 震荡等方式， 从而 制备本发明的能发射红外光的黑色光阻组合物。 由此， 具有上述组成的黑色 光阻组合物在保持常规的色度、 透过率等显示性能的基础上， 还能发射 5 ~ 15微米范围的远红外光线， 比辐射率为 0.35 ~ 0.95, 从而具有保健作用。 实施例
各实施例中所用原材料如下：
A、 着色剂： Raven 760 Ultra
B、 红外光发射材料：
B-1: 黑色电气石： 密度 3.06g/cm3, 折光率 1.62, 硬度 7
B-2: 生物炭： 比表面积 600m2/g, 密度 1.3g/cm3
B-3: 氧化铝： 纯度大于 99.9%
C、 溶剂
C-1 : 丙二醇单曱基醚醋酸酯 (PMA)
C-2: 3-乙氧基丙酸乙酯 (EEP)
C-3: 正丁醇 (n-BuOH)
D、 碱可溶性树脂
D-l : SB 401(Sartomer)
D-2: SB 404(Sartomer)
E、 乙烯性不饱和单体
E-l: EBE 350(氰特化工）
E-2: 双季戊四醇五 /六丙烯酸酯 DPHA (氰特化工）
F、 引发剂 F- 1： Irgacure 369(Ciba精化）
F-2: OXE-02(Ciba精化）
G、 其它添加剂
G-l : 附着力促进剂 A-186
G-2: 流平剂 BYK 333
H、 分散剂
H-l : BYK 161
H-2: Solsperse 32500
H-3: CN 2284
H-4: Solsperse 22000
着色混合材料的制备
实施例 1
将 5g分散剂 BYK 161加入至 95g溶剂丙二醇单曱基醚醋酸酯 (PMA)中， 向其加入 11. lg的氧化铝颗粒。 该混合物经搅拌均匀后， 置于砂磨机中研磨 粉碎至氧化铝的平均粒径为 17nm, 得到氧化铝纳米分散溶液。
将单体曱基丙烯酸曱酯、 苯乙烯、 马来酰亚胺 (l:l:l/mol)溶解于溶剂 PMA (单体：溶剂 =l:l/vol)中，并将 27.7g所得溶液加入至装有搅拌器、温度计、 通气管和滴液漏斗的四口瓶中， 使得混合溶液中氧化铝的重量比为 8%。
将偶氮二异戊腈溶解于 PMA中， 制成偶氮二异戊腈的 PMA饱和溶液， 并记录完全溶解时的百分比。 对上述四口瓶通入氮气， 在 35°C下， 边搅拌边 加入如上制得的偶氮二异戊腈的 PMA饱和溶液， 其量使得作为引发剂的偶 氮二异戊腈的净含量为上述单体总净含量的 1%。反应保持 30min。反应结束 后加入 lOOmL 5 °C的 PMA, 搅拌使反应物达到室温。
将上述反应物过滤， 并用 50mL PMA清洗滤出的固体三次， 并于 90°C干 燥 15min,得到经曱基丙烯酸曱酯-苯乙烯-马来酰亚胺共聚物改性的氧化铝颗 粒， 测得其平均粒径为 24nm。
将黑色颜料 RAVEN 760 ULTRA与上述经改性的氧化铝颗粒以 19:1的重 量比混合得到着色混合材料 -1。 实施例 2
以与实施例 1相同的方法制备着色混合材料 -2到着色混合材料 -10, 不同 之处在于黑色颜料与经改性的红外光发射材料的混合比如表 1中所示。
黑色光阻组合物的制备
实施例 3
将 8g Solsperse 22000、 75g Solsperse 32500和 40g CN 2284与 423.5g溶剂 PMA以搅拌方式混合均勾， 制得分散剂溶液。 将该溶液中加入 100g的由实 施例 1制得的着色混合材料 -1, 以搅拌方式将颜料充分润湿， 制得混合溶液。 采用砂磨机对该混合溶液进行研磨分散， 得到着色混合材料^：液 -1 , 其中 着色混合材料的百分比为 15.5%。
将碱可溶性树脂 D-1 (10%)、 D-2 (2%), 乙烯性不饱和单体 E-1 (10%)、 E-2 (3.8%),光引发剂 F-1 (0.007%), F-2 (0.008%)以及其它添加剂 G-1 (0.002%) 和 G-2 (0.013%)加入溶剂 C-2(30%)和 C-3(10%)的混合溶剂中， 搅拌至完全溶 解得到光固化溶液。 将上述制得的着色混合材料分散液 -1 加入光固化溶液 中， 经砂磨机研磨混合， 研磨期间补充溶剂 C-1 , 使得黑色光阻组合物中着 色混合材料的百分比为 15%, 且溶剂 C-1的百分比为 19.17%, 由此制得黑色 光阻组合物 -1。
实施例 4 ~ 12
分别采用与实施例 3相同的方法制备黑色光阻组合物 -2到黑色光阻组合 物 -10, 不同之处在于采用如表 1中所示组成比例。
黑色光阻组合物的应用
将实施例 3 ~ 12中制得的黑色光阻组合物 -1到 -10采用旋转涂布法涂布在 玻璃基板上。 将涂布有黑色光阻组合物的基板在 90 °C温度下烘烤 7分钟后， 采用照度为 180mJ/cm2的紫外线以 15秒的曝光时间对上述黑色光阻组合物进 行曝光。 将曝光后的玻璃基板在碱性显影液中显影后， 在 200°C温度下烘烤 20分钟， 形成厚度为 1.5μηι的黑色矩阵图形 1 ~ 10。
对所形成的各黑色矩阵图形进行红外线比辐射率 (IRE-1 型红外辐射测量 仪)及色度测定 (岛津 UV-2550), 结果示于以下表 1中。 表 1中"△，，表示综合 性能一般， "0"表示综合性能良好。
表 1
Figure imgf000012_0001
结合以上表格的结果可以看出， 当着色剂与红外光发射材料的比大于 6 时， 红外线比辐射率偏氏， 如实施例 3和实施例 4。 对于实施例 12, 由于着 色材料的含量偏低， 因此其中的着色剂含量偏低， 致使黑色光阻材料的光密 度低 (OD值小）。
当着色混合材料内红外光发射材料的含量低时， 光阻组合物的红外线比 辐射率也低， 随着着色混合材料内红外光发射材料含量的增加， 光阻组合物 的红外线比辐射率增大， 但均未对光阻材料的光密度造成明显影响。
未经表面处理和经表面处理的红外光发射材料对光阻稳定性的影响 对比例 1
将 5g BYK 161加入至 95g溶剂丙二醇单曱基醚醋酸酯 (PMA)中， 向其加入 11. lg的氧化铝颗粒。 该混合物经搅拌均匀后， 置于砂磨机中研磨 粉碎至氧化铝的平均粒径为 17nm, 得到氧化铝纳米分散溶液。 去除该氧化 铝纳米分散溶液中的溶剂， 得到氧化铝纳米颗粒。
将黑色颜料 RAVEN 760 ULTRA与上述氧化铝纳米颗粒以 19:1的重量比 混合得到着色混合材料。
按照实施例 3的方法制得对比黑色光阻组合物。
将实施例 3和对比例 1制得的两种黑色光阻组合物置于 0 ~ 4°C的避光环 境中， 观察光阻组合物的分层和沉淀现象。
对比黑色光阻组合物： 24小时后， 表面出现结皮现象， 且容器底部有少 量沉淀； 48小时后， 搅拌时出现大量结块， 固体颗粒团聚严重。
黑色光阻组合物 -1: 直至 48小时， 均未发现表面结皮或底部沉淀现象， 搅拌未出现结块及团聚现象。
综上所述， 根据本发明的能发射红外光的黑色光阻组合物通过添加经过 表面改性的红外光发射材料的纳米颗粒， 可发射具有保健作用的远红外光 线， 同时保持了常规的显示性能。

Claims

权利要求书
1、一种能发射红外光的黑色光阻组合物，其中所述能发射红外光的黑色 光阻组合物包括基于所述组合物总重的如下重量百分比的组分：
2% ~ 15%的着色混合材料、 30% ~ 90%的溶剂、 2% ~ 20%的碱可溶性树 脂、 2% ~ 20%的乙烯性不饱和单体、 0.01% ~ 1%的光引发剂和 0.005% ~ 0.02% 的其它添加剂；
其中，所述着色混合材料包括重量比为 19:1 ~ 1 : 1的着色剂和表面改性的 红外光发射材料。
2、根据权利要求 1所述的能发射红外光的黑色光阻组合物，其中所述着 色混合材料包括重量比为 6: 1 ~ 1: 1的着色剂和表面改性的红外光发射材料。
3、根据权利要求 1所述的能发射红外光的黑色光阻组合物，其中所述红 外光发射材料为选自电气石、 生物炭、 远红外陶瓷、 玉石粉、 氧化铝、 氧化 铜、 氧化银以及碳化硅中的一种或多种。
4、根据权利要求 3所述的能发射红外光的黑色光阻组合物，其中所述红 外光发射材料经聚合物材料表面改性。
5、根据权利要求 4所述的能发射红外光的黑色光阻组合物，其中所述聚 合物材料为曱基丙烯酸曱酯 -苯乙烯-马来酰亚胺的共聚物。
6、根据权利要求 1所述的能发射红外光的黑色光阻组合物，其中所述表 面改性的红外光发射材料具有 lnm ~ 200nm的平均粒径。
7、根据权利要求 3所述的能发射红外光的黑色光阻组合物，其中所述电 气石为黑色电气石， 且密度为 3.06 ~ 3.26g/cm3, 折光率为 1.62 ~ 1.64。
8、一种制备能发射红外光的黑色光阻组合物的方法，其中所述方法包括 如下步骤：
将红外光发射材料研磨并分散于溶剂中， 得到包含平均粒径为 lnm ~
200nm的红外光发射材料纳米粒子的纳米分散溶液；
用聚合物材料对所述纳米分散溶液中的红外光发射材料纳米粒子进行改 性， 随后去除溶剂， 得到经聚合物材料改性的红外光发射材料纳米粒子； 到着色混合材料， 并且
将所述着色混合材料与溶剂、 碱可溶性树脂、 乙烯性不饱和单体、 光引 发剂和其他添加剂混合， 得到能发射红外光的黑色光阻组合物。
9、 根据权利要求 8所述的制备能发射红外光的黑色光阻组合物的方法， 其中所述红外光发射材料为选自电气石、 生物炭、 远红外陶瓷、 玉石粉、 氧 化铝、 氧化铜、 氧化银以及碳化硅中的一种或多种。
10、根据权利要求 8所述的制备能发射红外光的黑色光阻组合物的方法， 其中所述聚合物材料为曱基丙烯酸曱酯 -苯乙烯-马来酰亚胺的共聚物。
11、 一种彩色滤光片， 包括由如权利要求 1至 7中任一项所述的能发射 红外光的黑色光阻组合物形成的黑色矩阵。
12、 一种显示器件， 包括如权利要求 11所述的彩色滤光片。
PCT/CN2013/089879 2013-04-28 2013-12-18 黑色光阻组合物、其制备方法、彩色滤光片和显示器件 WO2014176915A1 (zh)

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