CN109960109B - Dispersing agent, photosensitive resin composition and application of dispersing agent and photosensitive resin composition - Google Patents
Dispersing agent, photosensitive resin composition and application of dispersing agent and photosensitive resin composition Download PDFInfo
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- CN109960109B CN109960109B CN201711340447.3A CN201711340447A CN109960109B CN 109960109 B CN109960109 B CN 109960109B CN 201711340447 A CN201711340447 A CN 201711340447A CN 109960109 B CN109960109 B CN 109960109B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
- G02F1/133514—Colour filters
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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
- G03F7/004—Photosensitive materials
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The present disclosure relates to a dispersant and photosensitive resin composition and the use of both, the dispersant having the structural formula:wherein R is 1 Is methyl or hydrogen, R 2 Is methyl or hydrogen, R 3 Is a hydrocarbon group or an oxygen-containing hydrocarbon group, R 4 Is methyl or hydrogen, R 5 Is hydrocarbon or hydrogen, A ‑ Is an acid radical anion, n1, n2, n3 and n4 are the number of repeated units, n1 is 3-10, n2 is 5-20, n3 is 5-15, and n4 is 3-10. The dispersing agent provided by the disclosure has good dispersion stability to quantum dots, and the photosensitive resin composition has good heat resistance and developability.
Description
Technical Field
The present disclosure relates to a dispersant and a photosensitive resin composition and applications of both.
Background
The existing liquid crystal display has the problems of low display color gamut, low brightness, poor contrast and the like, the quantum dot is used as a novel semiconductor light-emitting nanomaterial, has the characteristics of narrow light-emitting spectrum, high light-emitting intensity and the like, and can improve the problems of the liquid crystal display when being applied to the liquid crystal display, so that the image quality can be remarkably improved, and the quantum dot combined with photosensitive resin is particularly applied to a color filter.
The problems of quantum dots applied to photosensitive resins are mainly the thermolabile nature of the quantum dots themselves, poor dispersibility in resins and difficulty in development.
Disclosure of Invention
The purpose of the present disclosure is to provide a dispersing agent and a photosensitive resin composition, and applications of both, the dispersing agent provided by the present disclosure has good dispersion stability to quantum dots, and the photosensitive resin composition has good heat resistance and developability.
In order to achieve the above object, the present disclosure provides a dispersant having the structural formula:
wherein R is 1 Is methyl or hydrogen, R 2 Is methyl or hydrogen, R 3 Is a hydrocarbon group or an oxygen-containing hydrocarbon group, R 4 Is methyl or hydrogen, R 5 Is hydrogen, benzyl or alkyl, A - Is an acid radical anion, n1, n2, n3 and n4 are the number of repeated units, n1 is 3-10, n2 is 5-20, n3 is 5-15, and n4 is 3-10.
Alternatively, the molecular weight of the dispersant is 3000-6000 and the acid value is 40-70mgKOH/g.
Alternatively, R 1 Is methyl, R 2 Is methyl, R 3 Is methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-dodecyl, 2-ethylhexyl, 2-hydroxyethyl, decyl, methyl sulfonate or isobornyl, R 4 Is methyl or hydrogen, A - Is formate, acetate, oleate, mercaptopropionate, mercaptobutyrate, oxalate, citrate, stearate, halide, dihydrogen phosphate or hydrogen sulfate.
Alternatively, n1 is 5-8, n2 is 8-15, n3 is 8-12, and n4 is 5-8.
The present disclosure also provides a photosensitive resin composition including quantum dots, an unsaturated bond-containing monomer, an alkali-soluble resin, an initiator, a solvent, and a dispersant provided by the present disclosure.
Optionally, based on the weight of the photosensitive resin composition, the weight content of each component in the photosensitive resin composition is as follows:
optionally, the photosensitive resin composition further comprises 0.01-0.5 wt% of an auxiliary agent based on the weight of the photosensitive resin composition, wherein the auxiliary agent is at least one selected from a leveling agent, a defoaming agent, a coupling agent, a hyperdispersant and a plasticizer.
Optionally, the quantum dot is at least one kind of quantum dot and carbon quantum dot selected from single core, core-shell, binary, ternary, quaternary and gradient alloy types composed of at least two elements of group IIB element, group VIA element, group IIIA element, group VA element and group IB element;
the monomer is selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, decyl acrylate, methyl acrylate sulfonate, isobornyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethylene glycol monomethyl ether acrylate propylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, decyl methacrylate, methyl methacrylate sulfonate, isobornyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, at least one of dipentaerythritol pentamethacrylate, dipentaerythritol hexamethyl acrylate, trimethylolpropane trimethacrylate, ethylene glycol monomethyl ether methacrylate, and propylene glycol dimethacrylate;
the alkali-soluble resin is at least one selected from methacrylate polymers, acrylate polymers, cycloolefin-maleic anhydride copolymers and vinyl ether-maleic anhydride copolymers;
the initiator is at least one selected from 2, 2-azobisisobutyronitrile, 2-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 1-azobis (cyclohexane-1-carbonitrile), diisobutyronitrile, benzoyl methyl ether, benzoyl diethyl ether, benzoyl isobutyl ether, biphenyl acyl, methyl phenylglyoxylate, benzoyl tosylate, diethoxyacetophenol, 2-hydroxy-2-methyl-1-phenylpropyl-1-one, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, p-tert-butyltrichloroacetophenone, benzophenone, isopropylthioxanthone, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide and benzyl dimethyl ketal;
the solvent is at least one selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol tertiary butyl ether, chloroform and xylene.
Optionally, the quantum dot is selected from CdSe, cdTe, cdS, znS, znSe, cdZnSe, cdZnS, inP, cuInS 2 、CdZnTe、CdZnSeS、CdSe/ZnS、CdSe/CdS、CdTe/ZnS、CdSe/CdS/ZnS, cdTe/CdS/ZnS, cdZnS/ZnS, cdZnSeS/ZnS, inP/ZnS, inGaP/ZnS and CuInS 2 At least one of ZnS.
The present disclosure also provides for the use of the dispersants provided by the present disclosure and/or the compositions provided by the present disclosure in the preparation of optical filters.
The dispersing agent provided by the disclosure can coat the surface of the quantum dot to improve the dispersion stability of the quantum dot in the photosensitive resin composition and further improve the heat resistance and the developability of the photosensitive resin composition.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a schematic diagram of an exemplary manner of coupling a dispersant and quantum dots provided by the present disclosure;
fig. 2 is a schematic diagram of an exemplary cross-linked network structure of the photosensitive resin composition provided by the present disclosure.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The present disclosure provides a dispersant having the structural formula:
wherein R is 1 Is methyl or hydrogen, R 2 Is methyl or hydrogen, R 3 Is a hydrocarbon group or an oxygen-containing hydrocarbon group, R 4 Is methyl or hydrogen, R 5 Is hydrogen, benzyl or alkyl, A - Is an acid radical anion, n1, n2, n3 and n4 are the number of repeated units, n1 is 3-10, n2 is 5-20, n35-15, n4 is 3-10; preferably, n1 is 5-8, n2 is 8-15, n3 is 8-12, and n4 is 5-8.
When the quantum dot photoresist is applied to the preparation of the optical filter, compared with the traditional optical filter, the color gamut and the brightness of a liquid crystal display can be greatly improved, but the quantum dot material is not heat-resistant, and the dispersibility, the stability and the developability in the photoresist are also poor, so that the luminous performance and the photoetching process of the quantum dot photoresist can be influenced, and as shown in fig. 1, the positively charged dispersing agent provided by the disclosure can be coated on the surface of the negatively charged quantum dot, so that the dispersion stability of the quantum dot is improved.
The dispersing agent disclosed by the disclosure is formed by copolymerizing four monomers and is an ionic polymer with charges, the molecular weight of the dispersing agent is preferably 3000-6000, and the acid value is preferably 40-70mgKOH/g.
According to the present disclosure, the aforementioned four monomers constituting the dispersant are respectively:
in the monomer (1), R 1 Preferably methyl, in which case the monomer (1) is dimethylaminoethyl methacrylate; the acrylate monomer (1) is added into the dispersing agent to enable the dispersing agent to be charged and stably connected with the quantum dots, so that the quantum dots have excellent dispersion stability in the photosensitive resin composition;
the monomer (2) is maleimide; the purpose of adding the maleimide monomer (2) to the dispersant is to make the photosensitive resin composition have excellent heat resistance and further to improve the dispersion stability of the system;
in the monomer (3), R 2 Preferably methyl, R 3 Preferably methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-dodecyl, 2-ethylhexyl, 2-hydroxyethyl, decyl, methyl sulfonate or isobornyl, in which case the monomers (3) are methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, respectivelyButyl, lauryl, 2-ethyl-hexyl, 2-hydroxyethyl, decyl, methyl or isobornyl methacrylates; the acrylic ester monomer (3) is added into the dispersing agent to improve the compatibility of the dispersing agent and the photosensitive resin composition, so as to further improve the dispersion stability of the quantum dot dispersing agent in the photosensitive resin composition;
in the monomer (4), R 4 Preferably methyl or hydrogen, more preferably methyl, in which case monomer (4) is a methacrylic monomer; the acrylic monomer (4) is added to the dispersant in order to improve the developability of the photosensitive resin composition, which means the solubility of the photosensitive resin in an alkaline developer such as KOH.
According to the present disclosure, the dispersant may be positively charged by acidification or quaternization, e.g., A - In the form of formate, acetate, oleate, mercaptopropionate, mercaptobutyrate, oxalate, citrate, stearate, halide, dihydrogen phosphate or hydrogen sulfate, and the acid used for acidification is formic acid, acetic acid, oleic acid, mercaptopropionic acid, mercaptobutyric acid, oxalic acid, citric acid, stearic acid, halogenated acids (e.g. hydrochloric acid, hydrogen fluoride, hydrogen bromide and hydrogen iodide), phosphoric acid or sulfuric acid, in which case R 5 Is H; the quaternizing agent may be methyl chloride, ethyl chloride, propyl chloride, methyl bromide, ethyl bromide, propyl bromide, dodecyl chloride, benzyl chloride or benzyl bromide, in which case A - Is halogen ion, R 5 Is alkyl or benzyl.
The present disclosure also provides a photosensitive resin composition including quantum dots, an unsaturated bond-containing monomer, an alkali-soluble resin, an initiator, a solvent, and a dispersant provided by the present disclosure. The photosensitive resin composition of the present disclosure may obtain a pattern through a process of gumming, exposure, development, etc. As shown in fig. 2, the photosensitive resin composition of the present disclosure is capable of fixing quantum dots by a dispersant of a crosslinked network structure, and has good heat resistance and developability.
In light of the present disclosure, one skilled in the art may formulate the proportions of the components in the photosensitive resin composition as desired, for example, the weight content of the components in the photosensitive resin composition may be:
according to the present disclosure, the photosensitive resin composition may further include 0.01 to 0.5 wt% of an auxiliary agent, which may be at least one selected from a leveling agent, an antifoaming agent, a coupling agent, a hyper-dispersant, and a plasticizer, in addition to the above components, which are well known to those skilled in the art, for example, a leveling agent for increasing leveling of a resin and reducing surface defects of a filter, a coupling agent for increasing adhesion of a resin to a substrate, and the like, based on the weight of the photosensitive resin composition. Further, the leveling agent is preferably a fluorine-containing surfactant, the coupling agent is preferably a silane coupling agent, and the silane coupling agent may be at least one selected from trimethoxysilylbenzoic acid, vinyltrimethoxysilane, vinyltriacetoxysilane, γ -methacryloxypropyl trimethoxysilane, γ -isocyanatopropyl triethoxysilane, γ -glycidyl propyl trimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and the like.
The quantum dots are well known to those skilled in the art in light of the present disclosure, and may be, for example, single-core, core-shell, binary, ternary, quaternary, and gradient alloy type quantum dots selected from at least two elements of group IIB, group VIA, group IIIA, group VA, and group IB elements, and at least one of carbon quantum dots, preferably quantum dots composed of group IIB and group VIA elements, and quantum dots composed of group VA and group IIIA elements, further preferably CdSe, cdTe, cdS, znS, znSe, cdZnSe, cdZnS, inP, cuInS 2 CdZnTe, cdZnSeS, cdSe/ZnS, cdSe/CdS, cdTe/ZnS, cdSe/CdS/ZnS, cdTe/CdS/ZnS, cdZnS/ZnS, cdZnSeS/ZnS, inP/ZnS, inGaP/ZnS and CuInS 2 At least one of ZnS; quantum dots can be directly bonded in the aqueous phaseThe surface ligand can be mercapto acid, or can be synthesized in the oil phase and then further converted to make the surface have carboxyl. Specifically, the mercapto acid may be at least one of thioglycollic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and N-acetyl-L-cysteine. Further preferably, the quantum dots are green light or red light quantum dots, and the optimal wavelength can be 525nm or 625nm. Because the quantum dots are connected with the dispersing agent through the electrostatic adsorption effect, the quantum dots can be dispersed into the dispersing agent first in the specific preparation process of the photosensitive resin composition, and then the compound of the quantum dots and the dispersing agent can be dispersed into the photosensitive resin composition.
Monomers containing unsaturation are well known to those skilled in the art, and, in accordance with the present disclosure, are meant to contain unsaturation, typically having more than three functionalities, to provide excellent crosslinkability, preferably from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, decyl acrylate, methyl acrylate, isobornyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethylene glycol monomethyl ether acrylate, propylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, decyl methacrylate, methyl methacrylate, isobornyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, monoethyl, diethylene glycol monomethacrylate, 1, 4-hexanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1-hexanediol dimethacrylate, 1-dimethacrylic acid, 1-butanediol dimethacrylate, at least one of pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, trimethylolpropane trimethacrylate, ethylene glycol monomethyl ether methacrylate and propylene glycol dimethacrylate.
The alkali-soluble resin is well known to those skilled in the art in light of the present disclosure, and may be, for example, at least one selected from the group consisting of (meth) acrylate-based polymers, cycloolefin-maleic anhydride copolymers, and vinyl ether-maleic anhydride copolymers; further preferable is a (meth) acrylic polymer, and specifically at least one of a (meth) acrylic acid/benzyl methacrylate copolymer, a (meth) acrylic acid/benzyl methacrylate/maleic anhydride copolymer, a (meth) acrylic acid/benzyl methacrylate/maleimide copolymer, a (meth) acrylic acid/benzyl methacrylate/styrene copolymer, and a (meth) acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer is possible.
The initiator is well known to those skilled in the art in light of the present disclosure and may be, for example, at least one selected from the group consisting of 2, 2-azobisisobutyronitrile, 2-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 1-azobis (cyclohexane-1-carbonitrile), diisobutyronitrile, benzoylmethyl ether, benzoylethyl ether, benzoylisobutyl ether, biphenyl acyl, phenylglyoxylic acid methyl ester, benzoyltosylate, diethoxyacetophenol, 2-hydroxy-2-methyl-1-phenylpropyl-1-one, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, p-tert-butyltrichloroacetophenone, benzophenone, isopropylthioxanthone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and benzyl dimethyl ketal.
The solvent is well known to those skilled in the art in light of the present disclosure, and may be, for example, at least one selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol t-butyl ether, chloroform, and xylene. Preferably at least one selected from ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, 2-hydroxyethyl propionate, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate.
The present disclosure also provides for the use of the provided dispersants and/or the compositions in the preparation of optical filters, specific preparation methods are well known to those skilled in the art, and the disclosure is not repeated.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereto.
Example 1 and comparative example 1
Adding 1.96g of cadmium stearate, 130mg of selenium powder and 70ml of octadecene into a flask, vacuumizing, filling nitrogen for protection, heating to 260 ℃, reacting at 260 ℃ for 40min, dropwise adding 5ml of oleic acid for continuous reaction for 20min, then cooling to room temperature, adding 5g of zinc stearate and 15ml of oleic acid, further heating to 310 ℃, dropwise adding 6ml of oleylamine, 6ml of dodecyl mercaptan and 50ml of octadecene, reacting for 2h, cooling to room temperature, and purifying a reactant by using absolute ethyl alcohol to obtain CdSe/ZnS quantum dot powder.
1.2g of CdSe/ZnS quantum dot powder synthesized in an oil phase is taken and dissolved in 10mL of normal hexane, 0.7g of sodium dodecyl glycerol ether carboxylate is added, centrifugal precipitation is carried out after stirring for 30 minutes, vacuum drying is carried out at 90 ℃ for 1 hour, thus obtaining quantum dot powder, and the quantum dot powder is dissolved in 10mL of deionized water.
Dispersant A is prepared by copolymerizing dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 3:6:5:3 and charging. The synthesis method of the dispersant A is as follows: 150g of butyl acetate and 1.5g of azobisisobutyronitrile were added into a reaction flask, and dissolved by stirring at normal temperature. Then 23.6g of dimethylaminoethyl methacrylate, 29.1g of maleimide, 32.5g of 2-hydroxyethyl methacrylate and 12.9g of methacrylic acid are added, stirring is carried out, the temperature is raised to 110 ℃ and the reaction is carried out for 3 hours, 2g of dodecyl mercaptan is added for continuous reaction for 20 minutes, the temperature is reduced to room temperature, 75g of methanol is used for precipitating the polymer, the polymer is dried at 90 ℃ in vacuum for 2 hours, the dispersing agent A is powder, the weight average molecular weight (measured by gel permeation chromatography) of the dispersing agent A is controlled to 4500-5500, and the acid value is 65mgKOH/g. 2.5g of the prepared dispersant A was dissolved in 10mL of propylene glycol monomethyl ether acetate (PMA), the quantum dot solution and the dispersant solution were mixed and stirred for 30 minutes, then 7mL of absolute ethanol was added dropwise to the mixed solution of quantum dot and dispersant to precipitate and centrifuged, and the precipitate was dried in vacuo at 90℃for 2 hours.
The complex of quantum dots and a dispersing agent is dispersed into a photosensitive resin composition consisting of propylene glycol monomethyl ether acetate (PMA, as a solvent), alkali-soluble resin (acrylic copolymer, sho-BSR-3), dipentaerythritol hexaacrylate (monomer), initiator (Basf Lucirin TPO), silane coupling agent (gamma-glycidyl ether propyl trimethoxysilane coupling agent) and fluorine-containing leveling agent (Dow Corning DC-7), and the specific compositions are shown in Table 1.
The contents of the remaining components and the preparation method of the composition in comparative example 1 were exactly the same as in example 1, except that the dispersant A was replaced with a polymeric dispersant DA (Pick BYK-164 dispersant, germany) having a similar molecular weight. The photosensitive resin compositions prepared in example 1 and comparative example 1 were subjected to photolithography under the same conditions, and the development time and the color change rate ΔEab under the condition of post-baking at 230℃for 20min, respectively, were tested, and the development time, which was the time taken to develop a pattern, was an index for evaluating the development property, and the smaller the development time, the better the development property of the composition was, and ΔEab was measured by using a Kenicam CM-5 spectrocolorimeter.
TABLE 1
Example 2 and comparative example 2
18g of zinc acetate dihydrate, 7.5g of cadmium acetate dihydrate and 3.6g of mercaptosuccinic acid are dissolved in 450ml of deionized water, and after vacuum pumping, nitrogen protection is introduced and the mixture is heated to 90 ℃. 1.5g of selenium powder and 2g of sodium borohydride are dissolved in 8ml of deionized water at normal temperature, and 5ml of supernatant is quickly injected into the reaction flask after the selenium powder is completely dissolved and reacts for 1h at 90 ℃. 1.5g of thioacetamide and 0.8g of mercaptosuccinic acid are taken and dissolved in 5ml of deionized water, the solution is dropwise added into the reaction liquid and reacts for 3 hours at 90 ℃, and the solution is cooled to room temperature and purified by acetone to obtain CdZnSe/ZnS quantum dot powder.
The preparation method of the dispersing agent B comprises the steps of preparing a polymer B by copolymerizing and charging dimethylaminoethyl acrylate, maleimide, isobornyl methacrylate and methacrylic acid according to a molar ratio of 3:5:5:4, wherein the preparation method of the dispersing agent B comprises the following steps: 140g of dimethylbenzene and 1.4g of dibenzoyl peroxide are taken and added into a reaction flask, and stirred at normal temperature for dissolution. Then 21.5g of dimethylaminoethyl acrylate, 24.3g of maleimide, 55.5g of isobornyl methacrylate and 17.2g of methacrylic acid are added, the mixture is stirred and heated to 120 ℃ and reacted for 2.5 hours, 2g of dodecyl mercaptan is added for continuous reaction for 20 minutes, the temperature is reduced to room temperature, 75g of methanol is used for precipitating the polymer and the polymer is dried at 90 ℃ in vacuum for 2 hours, the dispersion agent B is powder, the weight average molecular weight (measured by gel permeation chromatography) of the dispersion agent B is controlled between 4500 and 5500, and the acid value is 65mgKOH/g. 2g of mercaptosuccinic acid modified CdZnSe/ZnS quantum dot powder synthesized in an aqueous phase was taken and dissolved in 10mL of deionized water. 3g of the prepared dispersant B was dissolved in 10mL of propylene glycol monomethyl ether acetate (PMA), the quantum dot solution and the dispersant solution were mixed and stirred for 30 minutes, then 7mL of absolute ethanol was added dropwise to the mixed solution of quantum dot and dispersant to precipitate and centrifuged, and the precipitate was dried in vacuo at 90℃for 2 hours.
The complex of quantum dots and a dispersing agent was dispersed into a photosensitive resin composition composed of propylene glycol monomethyl ether acetate (PMA, as a solvent), an alkali-soluble resin (acrylic copolymer, sho-de BSR-3), dipentaerythritol hexaacrylate (monomer), an initiator (basf Lucirin TPO), a silane coupling agent (γ -glycidyl ether propyl trimethoxysilane coupling agent), and a fluorine-containing leveling agent (dakangnin DC-7), and the specific compositions are shown in table 2.
The contents of the remaining components and the preparation method of the composition in comparative example 2 were exactly the same as in example 2, except that the dispersant B was replaced with a polymer dispersant DB (Pick BYK-163 dispersant, germany) having a similar molecular weight. The photosensitive resin compositions prepared in example 2 and comparative example 2 were subjected to photolithography under the same conditions, and the development time and the color change rate ΔEab under post-baking conditions of 230℃and 20min, respectively, were tested.
TABLE 2
As can be seen from the comparative data in tables 1 and 2, the photosensitive resin compositions in examples have short development time, low color change rate, and excellent developability and heat resistance, and in addition, the photosensitive resin compositions in examples have no agglomeration phenomenon during the leaving and application processes, and exhibit excellent dispersion stability.
Claims (8)
1. A photosensitive resin composition, characterized in that the composition comprises quantum dots, an unsaturated bond-containing monomer, an alkali-soluble resin, an initiator, a solvent and a dispersant;
the structural formula of the dispersing agent is as follows:
wherein R is 1 Is methyl or hydrogen, R 2 Is methyl or hydrogen, R 3 Is a hydrocarbon group or an oxygen-containing hydrocarbon group, R 4 Is methyl or hydrogen, R 5 Is hydrogen, benzyl or alkyl, A - N1, n2, n3 and n4 are the number of repeating units, n1 is 3-10, n2 is 5-20, n3 is 5-15, and n4 is 3-10;
the weight content of each component in the photosensitive resin composition is as follows, based on the weight of the photosensitive resin composition:
2. the composition according to claim 1, wherein the dispersant has a molecular weight of 3000-6000 and an acid value of 40-70mgKOH/g.
3. The composition of claim 1, wherein R 1 Is methyl, R 2 Is methyl, R 3 Is methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-dodecyl, 2-ethylhexyl, 2-hydroxyethyl, decyl, methyl sulfonate or isobornyl, R 4 Is methyl or hydrogen, A - Is formate, acetate, oleate, mercaptopropionate, mercaptobutyrate, oxalate, citrate, stearate, halide, dihydrogen phosphate or hydrogen sulfate.
4. The composition of claim 1, wherein n1 is 5-8, n2 is 8-15, n3 is 8-12, and n4 is 5-8.
5. The composition of claim 1, wherein the photosensitive resin composition further comprises 0.01 to 0.5 wt% of an auxiliary agent, based on the weight of the photosensitive resin composition, the auxiliary agent being at least one selected from the group consisting of a leveling agent, an antifoaming agent, a coupling agent, a hyperdispersant, and a plasticizer.
6. The composition of claim 1, wherein the quantum dot is at least one selected from the group consisting of single core, core shell, binary, ternary, quaternary, and gradient alloy type quantum dots and carbon quantum dots consisting of at least two of group IIB elements, group VIA elements, group IIIA elements, group VA elements, and group IB elements;
the monomer is selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, decyl acrylate, methyl acrylate sulfonate, isobornyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethylene glycol monomethyl ether acrylate propylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, decyl methacrylate, methyl methacrylate sulfonate, isobornyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, at least one of dipentaerythritol pentamethacrylate, dipentaerythritol hexamethyl acrylate, trimethylolpropane trimethacrylate, ethylene glycol monomethyl ether methacrylate, and propylene glycol dimethacrylate;
the alkali-soluble resin is at least one selected from methacrylate polymers, acrylate polymers, cycloolefin-maleic anhydride copolymers and vinyl ether-maleic anhydride copolymers;
the initiator is at least one selected from 2, 2-azobisisobutyronitrile, 2-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 1-azobis (cyclohexane-1-carbonitrile), diisobutyronitrile, benzoyl methyl ether, benzoyl diethyl ether, benzoyl isobutyl ether, biphenyl acyl, methyl phenylglyoxylate, benzoyl tosylate, diethoxyacetophenol, 2-hydroxy-2-methyl-1-phenylpropyl-1-one, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, p-tert-butyltrichloroacetophenone, benzophenone, isopropylthioxanthone, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide and benzyl dimethyl ketal;
the solvent is at least one selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol tertiary butyl ether, chloroform and xylene.
7. The composition of claim 1, wherein the quantum dot is selected from CdSe, cdTe, cdS, znS, znSe, cdZnSe, cdZnS, inP, cuInS 2 CdZnTe, cdZnSeS, cdSe/ZnS, cdSe/CdS, cdTe/ZnS, cdSe/CdS/ZnS, cdTe/CdS/ZnS, cdZnS/ZnS, cdZnSeS/ZnS, inP/ZnS, inGaP/ZnS and CuInS 2 At least one of ZnS.
8. Use of a composition according to any one of claims 1-7 for the preparation of a filter.
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| US4224398A (en) * | 1979-05-29 | 1980-09-23 | Richardson Graphics Company | Photopolymerizable latex systems |
| CN101541898A (en) * | 2007-06-21 | 2009-09-23 | 三菱化学株式会社 | Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display and organic EL display |
| CN101646977A (en) * | 2007-11-08 | 2010-02-10 | 株式会社Lg化学 | Colored dispersion, photoresist composition and black matrix |
| CN103772872A (en) * | 2013-12-27 | 2014-05-07 | Tcl集团股份有限公司 | Quantum dot/acrylate polymer nanocrystal complex, preparation method of quantum dot/acrylate polymer nanocrystal complex, and colored conversion coating |
| CN102719148B (en) * | 2007-06-21 | 2015-04-08 | 三菱化学株式会社 | Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display and organic el display |
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| US4224398A (en) * | 1979-05-29 | 1980-09-23 | Richardson Graphics Company | Photopolymerizable latex systems |
| CN101541898A (en) * | 2007-06-21 | 2009-09-23 | 三菱化学株式会社 | Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display and organic EL display |
| CN102719148B (en) * | 2007-06-21 | 2015-04-08 | 三菱化学株式会社 | Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display and organic el display |
| CN101646977A (en) * | 2007-11-08 | 2010-02-10 | 株式会社Lg化学 | Colored dispersion, photoresist composition and black matrix |
| CN103772872A (en) * | 2013-12-27 | 2014-05-07 | Tcl集团股份有限公司 | Quantum dot/acrylate polymer nanocrystal complex, preparation method of quantum dot/acrylate polymer nanocrystal complex, and colored conversion coating |
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