CN115010849B - Solvent-free high-refractive-index optical material and preparation method and application thereof - Google Patents

Solvent-free high-refractive-index optical material and preparation method and application thereof Download PDF

Info

Publication number
CN115010849B
CN115010849B CN202210562408.2A CN202210562408A CN115010849B CN 115010849 B CN115010849 B CN 115010849B CN 202210562408 A CN202210562408 A CN 202210562408A CN 115010849 B CN115010849 B CN 115010849B
Authority
CN
China
Prior art keywords
refractive index
high refractive
acrylate
solvent
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210562408.2A
Other languages
Chinese (zh)
Other versions
CN115010849A (en
Inventor
邹菁
江吉周
王海涛
项坤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Institute of Technology
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CN202210562408.2A priority Critical patent/CN115010849B/en
Publication of CN115010849A publication Critical patent/CN115010849A/en
Application granted granted Critical
Publication of CN115010849B publication Critical patent/CN115010849B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2255—Oxides; Hydroxides of metals of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a solvent-free high-refractive-index optical material, which comprises the following components in percentage by weight: 40-70 parts of high refractive index dispersion liquid, 10-20 parts of acrylic monomer, 5-15 parts of oligomer, 2-10 parts of photoinitiator and 1-5 parts of cross-linking agent; the solvent-free high refractive index composition provided by the invention takes acrylic monomers and polyurethane/polyurea ester oligomers as main components, and is doped with high refractive index inorganic nano particles to prepare solvent-free composition; therefore, in the process of photocuring film formation, the process step of removing the solvent is not needed, and compared with the conventional solvent type high-refractive-index material, the whole process flow is simplified; on the other hand, the molecular chain of the high refractive index composition contains polyurethane and polyurethane chain links, and when the high refractive film prepared by using the polyurethane chain links is subjected to bending deformation, a large number of hydrogen bonds in polyurethane and polyurethane can interact, so that the film is effectively prevented from being broken, and the polyurethane chain has bright application prospect in optoelectronic devices.

Description

Solvent-free high-refractive-index optical material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an optical material, a preparation method and application thereof.
Background
The AMOLED display technology has become the mainstream technology of mobile display devices such as mobile phones and watches, and gradually permeates into the fields of flat plates, notebook computers, televisions and the like, so that the light-emitting efficiency of the AMOLED display is effectively improved, and the microlens array technology based on high-low refractive index materials becomes a hot spot of current research.
However, the high refractive index polymeric optical materials currently reported suffer from a number of drawbacks, both synthetically and in terms of performance. For example, high refractive index polymeric optical materials are typically applied to large amounts of organic solvents during the preparation process, and the solvents need to be removed during the later film formation process, which means not only more complicated process steps, but also problems of solvent evaporation and contamination, film solvent residue, etc., and even further influences on the hardness, lifetime, etc. of the film. In addition, the problems that the high refraction film layer generates tensile deformation in the screen folding process, so that folds, cracks and the like are generated on the screen are also solved. Based on this, development of a more simple, better performing high refractive index optical material is urgently required for large-scale commercial applications.
Disclosure of Invention
The invention aims to provide a solvent-free high-refractive-index optical material, a preparation method and application thereof, and solves the problems of poor performance and the like of a high-refractive-index film caused by complex curing process and residual solvent of the high-refractive-index material.
In order to achieve the above purpose, the following technical scheme is adopted:
a solvent-free high refractive index optical material comprises the following components in percentage by weight:
40-70 parts of high refractive index dispersion liquid, 10-20 parts of acrylic monomer, 5-15 parts of oligomer, 2-10 parts of photoinitiator and 1-5 parts of cross-linking agent.
According to the scheme, the oligomer is one of the following structural formulas:
wherein R is 1 Selected from disulfide units, C 1 -C 6 Chain alkyl, C 1 -C 6 Chain alkoxy, C 3 -C 6 Cyclic alkyl of C 6 -C 18 Aryl, C substituted or unsubstituted by hetero atoms 2 -C 5 One of the cyclic olefins.
Optimally, the C 6 -C 18 Aryl of (2) is one of phenyl, biphenyl, naphthyl and anthryl;
the C being substituted or unsubstituted by hetero atoms 2 -C 5 The cycloolefin is cyclopentadiene substituted or unsubstituted by hetero atoms, and the hetero atoms are one of nitrogen, oxygen, sulfur and selenium.
According to the scheme, the acrylic monomer is C 1 -C 30 Mono-functional (meth) acrylates or C 2 -C 30 Is described herein).
Optimally, the monofunctional (methyl) acrylate is one of 2-hydroxyethyl (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, butyl acrylate, isooctyl acrylate, benzyl (methyl) acrylate and phenyl (methyl) acrylate;
the difunctional (methyl) acrylate is one of ethylene glycol di (methyl) acrylate, 1, 3-propylene glycol di (methyl) acrylate, diethylene glycol di (methyl) acrylate, tetraethylene glycol di (methyl) acrylate, 1, 6-hexanediol di (methyl) acrylate and 1, 9-nonanediol di (methyl) acrylate.
According to the scheme, the high refractive index dispersion liquid contains 50-63% of nano particles by mass percent; the inorganic nano particles are oxides or sulfides of one or more of metals Ti, zr, zn, ce, ta, bi, nb, in, hf, sn, mo, sb, nd; the grain diameter is 1-50 nm.
According to the scheme, the photoinitiator is a free radical photoinitiator or a cationic photoinitiator.
Optimally, the free radical photoinitiator is one or more of benzophenone, benzoin dimethyl ether, benzil dimethyl ether, isopropyl thioxanthone, 2,4,6, -trimethylbenzoyl diphenyl phosphine oxide, phenyl bis (2, 4,6, -trimethylbenzoyl) phosphine oxide and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone;
the cationic photoinitiator is one or more of diphenyl hexafluoroantimonate iodonium salt, diphenyl hexafluoroarsonate iodonium salt, diphenyl hexafluorophosphate iodonium salt, fluoboric acid iodonium salt, aryl diazonium salt and Su Mao ferric salt.
According to the scheme, the cross-linking agent is one of pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol triacrylate, diisoamyl tetraacrylate, tri (2-hydroxyethyl) isocyanuric acid triacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate and dipentaerythritol penta/hexaacrylate.
The preparation method of the solvent-free high-refractive-index optical material comprises the following steps:
and (3) adding the photoinitiator into the high refractive index dispersion liquid, fully mixing, and then adding the acrylic monomer, the cross-linking agent and the oligomer, and fully stirring to obtain the solvent-free high refractive index composition.
The application of the solvent-free high-refractive-index optical material as an optical functional layer in an optoelectronic device comprises the steps of flash evaporation, ink-jet printing, deposition, screen printing, spin coating or doctor blade coating of the solvent-free high-refractive-index optical material, and then ultraviolet light irradiation to form the solvent-free high-refractive-index optical material.
Compared with the prior art, the invention has the following beneficial effects:
the solvent-free high refractive index composition provided by the invention is prepared by taking acrylic monomers and polyurethane/polyurea ester oligomers as main components and doping high refractive index inorganic nano particles, and does not contain solvent. On one hand, the high refractive index composition does not contain solvent, so that the process step of removing the solvent is not needed in the photo-curing film forming process, compared with the conventional solvent type high refractive index material, the whole process flow is simplified, and meanwhile, the adverse effects of environment pollution and solvent residues caused by solvent volatilization on the hardness and service life of the high refractive index film are effectively avoided. On the other hand, the molecular chain of the high refractive index composition contains polyurethane and polyurethane chain links, so that when the high refractive film prepared by using the high refractive index composition is subjected to bending deformation, a large number of hydrogen bonds in polyurethane and polyurethane can interact, thereby effectively avoiding the film from cracking, and even the broken molecular chain can be bonded again due to the induction of the large number of hydrogen bonds, so that the film material can be automatically repaired. The composition provided by the invention is an excellent high-refraction optical material, and has bright application prospect in optoelectronic devices.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a specific embodiment, a solvent-free high refractive index optical material is provided, which comprises the following components in percentage by weight:
40-70 parts of high refractive index dispersion liquid, 10-20 parts of acrylic monomer, 5-15 parts of oligomer, 2-10 parts of photoinitiator and 1-5 parts of cross-linking agent.
Specifically, the oligomer is one of the following structural formulas:
wherein R is 1 Selected from disulfide units, C 1 -C 6 Chain alkyl, C 1 -C 6 Chain alkoxy, C 3 -C 6 Cyclic alkyl of C 6 -C 18 Aryl, C substituted or unsubstituted by hetero atoms 2 -C 5 One of the cyclic olefins.
Optimally, the C 6 -C 18 Aryl of (2) is one of phenyl, biphenyl, naphthyl and anthryl;
the C being substituted or unsubstituted by hetero atoms 2 -C 5 The cycloolefin is cyclopentadiene substituted or unsubstituted by hetero atoms, and the hetero atoms are one of nitrogen, oxygen, sulfur and selenium.
Specifically, the acrylic monomer is C 1 -C 30 Mono-functional (meth) acrylates or C 2 -C 30 Is a difunctional (meth) acrylate of (a) a (meth) acrylate.
Optimally, the monofunctional (methyl) acrylate is one of 2-hydroxyethyl (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, butyl acrylate, isooctyl acrylate, benzyl (methyl) acrylate and phenyl (methyl) acrylate;
the difunctional (methyl) acrylate is one of ethylene glycol di (methyl) acrylate, 1, 3-propylene glycol di (methyl) acrylate, diethylene glycol di (methyl) acrylate, tetraethylene glycol di (methyl) acrylate, 1, 6-hexanediol di (methyl) acrylate and 1, 9-nonanediol di (methyl) acrylate.
Specifically, the high refractive index dispersion liquid is a dispersion liquid of 50-63% of nano particles in mass fraction in acrylic resin; the inorganic nano particles are oxides or sulfides of one or more of the metals Ti, zr, zn, ce, ta, bi, nb, in, hf, sn, mo, sb, nd, the particle size is 1-50 nm, and the optimized particle size is 10-25nm. The acrylic resin comprises phenoxybenzyl acrylate, biphenyl methanol acrylate or o-phenylphenoxyethyl acrylate. Such as high refractive index dispersion MA67, MA69, MA70 or MA71, commercially available from KC Tech company in korea.
Specifically, the photoinitiator is a free radical photoinitiator or a cationic photoinitiator.
Optimally, the free radical photoinitiator is one or more of benzophenone, benzoin dimethyl ether, benzil dimethyl ether, isopropyl thioxanthone, 2,4,6, -trimethylbenzoyl diphenyl phosphine oxide, phenyl bis (2, 4,6, -trimethylbenzoyl) phosphine oxide and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone;
the cationic photoinitiator is one or more of diphenyl hexafluoroantimonate iodonium salt, diphenyl hexafluoroarsonate iodonium salt, diphenyl hexafluorophosphate iodonium salt, fluoboric acid iodonium salt, aryl diazonium salt and Su Mao ferric salt.
Specifically, the cross-linking agent is one of pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol triacrylate, diisoamyl tetraacrylate, tri (2-hydroxyethyl) isocyanurate triacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate and dipentaerythritol penta/hexaacrylate.
The preparation method of the solvent-free high-refractive-index optical material comprises the following steps:
and (3) fully mixing the heated photoinitiator in the high refractive index dispersion liquid, and fully stirring the acrylic monomer, the crosslinking agent and the oligomer to obtain the solvent-free high refractive index composition.
The application of the solvent-free high-refractive-index optical material as an optical functional layer in an optoelectronic device comprises the steps of flash evaporation, ink-jet printing, deposition, screen printing, spin coating or doctor blade coating of the solvent-free high-refractive-index optical material, and then ultraviolet light irradiation to form the solvent-free high-refractive-index optical material.
Specific embodiments provide synthetic examples of oligomers:
synthesis example 1: synthesis of cpd-1
In a three-necked flask equipped with a thermometer, a condenser and a nitrogen inlet tube, dried ethylene glycol (18.62 g,0.3 mol) and dried isocyanatoethyl methacrylate (31.03 g,0.2 mol) and dibutyltin dilaurate (0.12 g,2 mol) were added, and after thorough mixing, the mixture was slowly warmed to 80℃under nitrogen atmosphere to react for 2 hours, and then 1-isocyanato-2-methoxyethane (20.22 g,0.2 mol) was added to react for 2 hours, cooled to room temperature and purified by column chromatography to obtain 36.93g of cpd-1, yield 58% and relative molecular mass of the compound measured by a mass spectrometer was 318.3305.
Synthesis example 2: synthesis of cpd-2
Into a three-necked flask equipped with a thermometer, a condenser and a nitrogen inlet tube, dry (2- (acryloyloxy) ethyl) carbamic acid (63.65 g,0.4 mol), methylene chloride (29.44 g,0.3 mol) and triethylamine (24.28 g,0.24 mol) were added, an ice bath was introduced under nitrogen protection, sulfur dichloride (20.59 g,0.2 mol) was slowly added dropwise, the reaction was continued for 1 hour after the dropwise addition, the reaction solution was distilled under reduced pressure, and then purified by column chromatography to obtain 54.45g of cpd-2, the yield was 80%, and the relative molecular weight of the compound was 340.3702 as measured by a mass spectrometer.
Synthesis example 3: synthesis of cpd-3
In a three-neck flask equipped with a thermometer, a condenser and a nitrogen inlet pipe, dry 1, 3-cyclobutanediol (17.62 g,0.2 mol) and dry ethyl isocyanate acrylate (56.45 g,0.4 mol) and dibutyltin dilaurate (0.12 g,2 mmol) are added, after being fully mixed, the mixture is slowly heated to 80 ℃ to react for 2 hours under the atmosphere of nitrogen, cooled to room temperature and purified by column chromatography, 51.11g of cpd-3 can be obtained, the yield is 69%, and the relative molecular weight of the compound measured by a mass spectrometer is 370.3546.
Synthesis example 4: synthesis of cpd-4
In a three-necked flask equipped with a thermometer, a condenser and a nitrogen inlet tube, dried naphthalenediol (32.03 g,0.2 mol) and dried isocyanatoethyl methacrylate (62.06 g,0.4 mol) and dibutyltin dilaurate (0.12 g,2 mmol) were added, and after thorough mixing, the mixture was slowly warmed to 80℃under nitrogen atmosphere to react for 2 hours, cooled to room temperature and purified by column chromatography to obtain 70.57g of cpd-4 with a yield of 75% and a relative molecular mass of 470.4825 as measured by a mass spectrometer.
Synthesis example 5: synthesis of cpd-5
In a three-neck flask equipped with a thermometer, a condenser and a nitrogen inlet pipe, dry p-phenylenediamine (32.44 g,0.3 mol) is completely dissolved in dry tetrahydrofuran solvent, the temperature is raised to 50 ℃, dry isocyanatoethylacrylamide (28.03 g,0.2 mol) is added for stirring reaction for 1h, 1-isocyanato-2-methoxyethane (20.22 g,0.2 mol) is added for stirring reaction for 1h, the temperature is reduced to room temperature, column chromatography purification is carried out, 38.43g cpd-5 is obtained, the yield is 55%, and the relative molecular weight of the compound measured by a mass spectrometer is 349.3866.
Synthesis example 6: synthesis of cpd-6
In a three-necked flask equipped with a thermometer, a condenser and a nitrogen inlet pipe, dried 1, 3-cyclohexanediamine (34.26 g,0.3 mol) was completely dissolved in a dried tetrahydrofuran solvent, the temperature was raised to 50 ℃, dried (2-isocyanatoethyl) methacrylamide (30.83 g,0.2 mol) was added and stirred for reaction for 1 hour, 1-isocyanato-2-methoxyethane (20.22 g,0.2 mol) was further added and stirred for reaction for 1 hour, the temperature was lowered to room temperature, and column chromatography purification was carried out, whereby 36.95g of cpd-6 was obtained, the yield was 50%, and the relative molecular mass of the compound was 369.4711 as measured by a mass spectrometer.
Synthesis example 7: synthesis of cpd-7
In a three-neck flask equipped with a thermometer, a condenser and a nitrogen inlet pipe, dry cyclopentyl-3, 5-diene-1, 3-diamine (19.22 g,0.2 mol) is completely dissolved in dry tetrahydrofuran solvent, the temperature is raised to 50 ℃, dry ethyl-acrylamide isocyanate (56.06 g,0.4 mol) is added, stirring reaction is carried out for 1h, the temperature is reduced to room temperature, column chromatography purification is carried out, 47.43g of cpd-7 can be obtained, the yield is 63%, and the relative molecular mass of the compound measured by a mass spectrometer is 376.4225.
Synthesis example 8: synthesis of cpd-8
In a three-necked flask equipped with a thermometer, a condenser and a nitrogen inlet pipe, dry 2- (aminooxy) ethane-1-amine (36.85 g,0.2 mol) was completely dissolved in dry tetrahydrofuran solvent, the temperature was raised to 50 ℃, dry (2-isocyanatoethyl) methacrylamide (61.66 g,0.4 mol) was added and stirred for reaction for 1h, cooled to room temperature, and purified by column chromatography to obtain 53.05g of cpd-8 with a yield of 69%, and the relative molecular mass of the compound measured by a mass spectrometer was 384.4408.
Synthesis example 9: synthesis of cpd-9
In a three-necked flask equipped with a thermometer, a condenser and a nitrogen inlet tube, dry ethylene glycol (12.41 g,0.2 mol) and dry ethyl isocyanate acrylate (28.22 g,0.2 mol) and dibutyltin dilaurate (0.12 g,2 mmol) were added, and after thorough mixing, the temperature was slowly raised to 80℃under nitrogen atmosphere to react for 2 hours, cooled to room temperature, and purified by column chromatography to obtain 30.48g of the above comparative product, yield 75%, and the relative molecular mass of the compound measured by a mass spectrometer was 203.1872.
Example 1
At 70g, 50% by weight ZrO 2 To the high refractive index dispersion of (2), 4, 6-trimethylbenzoyl) phosphine oxide heated to 60℃was added and thoroughly mixed, then 20g of 2-hydroxyethyl acrylate and 15g of cpd-1 were added and thoroughly stirred, then 5g of di-pentanetetraol hexaacrylate was added and stirred at room temperature for 2 hours, thereby obtaining a solvent-free high refractive index composition.
Example 2
At 50g of ZrO containing 50% by weight 2 To the high refractive index dispersion of (2), 4, 6-trimethylbenzoyl) phosphine oxide heated to 60℃was added and thoroughly mixed, then 20g of 2-hydroxyethyl acrylate and 15g of cpd-1 were added and thoroughly stirred, then 5g of di-pentanetetraol hexaacrylate and 0.5g of BYK-358 from Pick auxiliary agent (Shanghai) were added and stirred at room temperature for 2 hours, whereby a solvent-free high refractive index composition was obtained.
Example 3
At 70g, 50% by weight ZrO 2 To the high refractive index dispersion of (2) a solvent-free high refractive index composition was obtained by adding 10g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide heated to 60℃and thoroughly mixing, then adding 20g of 2-hydroxyethyl acrylate and 15g of cpd-2 and thoroughly stirring, then adding 5g of diisoamyl tetrahexaacrylate and stirring at room temperature for 2 hours.
Example 4
At 70g, 50% by weight CeO was contained 2 To the high refractive index dispersion of (2) a solvent-free high refractive index composition was obtained by adding 10g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide heated to 60℃and thoroughly mixing, then adding 20g of 2-hydroxyethyl acrylate and 15g of cpd-2 and thoroughly stirring, then adding 5g of diisoamyl tetrahexaacrylate and stirring at room temperature for 2 hours.
Example 5
At 70g contain50% by weight of TiO 2 To the high refractive index dispersion of (2) was added 10g of benzophenone heated to 60℃and thoroughly mixed, then 10g of butyl acrylate, 10g of ethylene glycol di (meth) acrylate and 15g of cpd-3 were added and stirred thoroughly, then 5g of pentaerythritol tetraacrylate was added and stirred at room temperature for 2 hours, thereby obtaining a solvent-free high refractive index composition.
Example 6
At 70g, 63% by weight of TiO 2 To the high refractive index dispersion of (2) was added 10g of benzophenone heated to 60℃and thoroughly mixed, followed by adding 5g of isooctyl acrylate, 15g of 1, 3-propanediol di (meth) acrylate and 15g of cpd-4 and thoroughly stirring, and then adding 5g of trimethylolpropane triacrylate and stirring at room temperature for 2 hours, whereby a solvent-free high refractive index composition was obtained.
Example 7
To 70g of a high refractive index dispersion containing 50% by weight of ITO, 10g of benzil dimethyl ether heated to 60℃was added and thoroughly mixed, 10g of phenyl (meth) acrylate, 10g of diethylene glycol di (meth) acrylate and 15g of cpd-5 were added and thoroughly stirred, and then 5g of di (trimethylolpropane) tetraacrylate was added and stirred at room temperature for 2 hours, whereby a solvent-free high refractive index composition was obtained.
Example 8
At 70g MoO containing 50% wt 3 To the high refractive index dispersion of (2) was added 10g of isopropyl thioxanthone heated to 60℃and thoroughly mixed, 10g of benzyl acrylate, 10g of 1, 6-hexanediol di (meth) acrylate and 15g of cpd-6 were further added and thoroughly stirred, and then 5g of propoxylated glycerol triacrylate was added and stirred at room temperature for 2 hours, whereby a solvent-free high refractive index composition was obtained.
Example 9
At 70g containing 50% by weight of Ta 2 O 5 Adding 10g isopropyl thioxanthone heated to 60deg.C, mixing, adding 20g diethylene glycol monoethyl ether (meth) acrylate and 15g cpd-7, stirring, adding 5g pentaerythritol triacrylate, stirring at room temperature for 2 hr to obtain solvent-free high refractive indexAn emissivity composition.
Example 10
At 70g containing 63% wt HfO 2 To the high refractive index dispersion of (2) benzyl 2-dimethylamino 1- (4-morpholinophenyl) butanone heated to 60℃was added and thoroughly mixed, then 5g of 2-hydroxyethyl (meth) acrylate, 15g of 1, 9-nonanediol di (meth) acrylate and 15g of cpd-8 were added and thoroughly stirred, then 5g of propoxylated glycerol triacrylate was added and stirred at room temperature for 2 hours, thereby obtaining a solvent-free high refractive index composition.
Comparative example 1
At 70g, 50% by weight ZrO 2 To the high refractive index dispersion of (2), 4, 6-trimethylbenzoyl) phosphine oxide heated to 60℃was added and thoroughly mixed, then 20g of 2-hydroxyethyl acrylate and 15g of cpd-9 were added and thoroughly stirred, then 5g of diisoamyl tetrahexaacrylate was added and stirred at room temperature for 2 hours, whereby a solvent-free high refractive index composition was obtained.
Comparative example 2
At 70g, 50% by weight ZrO 2 To the high refractive index dispersion of (2), 4, 6-trimethylbenzoyl) phosphine oxide heated to 60℃was added and thoroughly mixed, and then 40g of diethylene glycol diethyl ether acetate, 20g of 2-hydroxyethyl acrylate and 15g of cpd-1 were added and thoroughly stirred, and then 5g of diisoamyl tetrahexaacrylate was added and stirred at room temperature for 2 hours, whereby a corresponding solvent-type high refractive index composition was obtained.
The viscosity of the solvent-free high refractive index compositions prepared in examples 1 to 10 and comparative examples 1 to 2 was measured with a viscometer, respectively.
The solvent-free high refractive index compositions prepared in examples 1 to 10 and comparative examples 1 to 2 were coated on a quartz substrate using an inkjet printing technique of 5um, and the substrate was dried in a vacuum oven for 30 minutes, and then put into a UV curing machine at about 2000mJ/cm 2 The high refractive index composition was irradiated with the intensity of the light to cure to form a high refractive film, the refractive index was measured with an Abbe refractometer, the hardness was measured with a durometer, the haze was measured with a haze meter, and the elongation at break was measured with a tensile machineThe long rate, the width of the healed scratch after healing for 4 hours at room temperature for the same initial scratch width of the high refractive film was measured by an optical microscope, and the self-healing efficiency thereof was calculated according to the formula (healed scratch width/initial scratch width).
The solvent-free high refractive index compositions prepared in examples 1 to 10 and comparative examples 1 to 2 were coated on a transparent cathode of an OLED device at 60nm using an inkjet printing technique, dried in a vacuum drying oven for 30 minutes, and then dried at about 2000mJ/cm 2 The high refractive index composition was irradiated to form a high refractive index layer in the light emitting direction of the OLED device, which was measured at 10mA/cm using Keithley2400, respectively, with the OLED device without the high refractive index layer 2 The illumination intensity is calculated to obtain the light-emitting efficiency improvement ratio of the high-refraction resin optical material. The test results are described in the following table.
As can be seen from the above table, the viscosity of the solvent-free high refractive index compositions prepared in examples 1 to 10 of the present invention is suitable for the inkjet printing process, and compared with comparative example 1, the physical stretching resistance and the extrusion deformation resistance of the film are stronger due to the self-repairing effect of hydrogen bonds, and compared with comparative example 2, the film has good film forming characteristics due to the absence of solvent, the film forming process is simple, no solvent residue exists in the film prepared by photo-curing, the refractive index, the haze, the hardness and other properties of the prepared film are remarkably improved, the refractive index is kept near 1.7 in the visible light range, the hardness of the cured film is more than 1H, and in addition, the physical stretching resistance, the extrusion deformation resistance and the light-emitting property of the film are also greatly improved, the comprehensive performance is excellent, and the film has bright application prospects in the field of optoelectronic display.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, various simple modifications can be made to the technical solution of the invention, including that each technical feature is combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, which falls within the protection scope of the invention.

Claims (8)

1. The solvent-free high-refractive-index optical material is characterized by comprising the following components in parts by weight:
40-70 parts of high refractive index dispersion liquid, 10-20 parts of acrylic monomer, 5-15 parts of oligomer, 2-10 parts of photoinitiator and 1-5 parts of crosslinking agent; the oligomer is one of the following structural formulas:
；/>；
；/>；
；/>；
；/>；
wherein R is 1 Selected from disulfide units, C 1 -C 6 Chain alkyl, C 1 -C 6 Chain alkoxy, C 3 -C 6 Cyclic alkyl, C 6 -C 18 Aryl, C substituted or unsubstituted by hetero atoms 2 -C 5 One of the cyclic olefins; n is equal to 1;
the high refractive index dispersion liquid is dispersion liquid of inorganic nano particles with the mass fraction of 50-63% in acrylic resin; the inorganic nanoparticles are oxides or sulfides of one or more of the metals Ti, zr, zn, ce, ta, bi, nb, in, hf, sn, mo, sb, nd.
2. The solvent-free high refractive index optical material according to claim 1, wherein said C 6 -C 18 Aryl of (2) is one of phenyl, biphenyl, naphthyl and anthryl;
the C being substituted or unsubstituted by hetero atoms 2 -C 5 The cycloolefin is cyclopentadiene substituted or unsubstituted by hetero atoms, and the hetero atoms are one of nitrogen, oxygen, sulfur and selenium.
3. The solventless high refractive index optical material of claim 1 wherein said acrylic monomer is C 1 -C 30 Mono-functional (meth) acrylates or C 2 -C 30 Is a difunctional (meth) acrylate of (a) a (meth) acrylate;
the monofunctional (methyl) acrylic ester is one of 2-hydroxyethyl (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylic ester, butyl acrylate, isooctyl acrylate, benzyl (methyl) acrylate and phenyl (methyl) acrylate;
the difunctional (methyl) acrylate is one of ethylene glycol di (methyl) acrylate, 1, 3-propylene glycol di (methyl) acrylate, diethylene glycol di (methyl) acrylate, tetraethylene glycol di (methyl) acrylate, 1, 6-hexanediol di (methyl) acrylate and 1, 9-nonanediol di (methyl) acrylate.
4. The solventless high refractive index optical material of claim 1 wherein said photoinitiator is a free radical photoinitiator or a cationic photoinitiator;
the free radical photoinitiator is one or more of benzophenone, benzoin dimethyl ether, benzil dimethyl ether, isopropyl thioxanthone, 2,4,6, -trimethylbenzoyl diphenyl phosphine oxide, phenyl bis (2, 4,6, -trimethylbenzoyl) phosphine oxide and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone;
the cationic photoinitiator is one or more of diphenyl hexafluoroantimonate iodonium salt, diphenyl hexafluoroarsonate iodonium salt, diphenyl hexafluorophosphate iodonium salt, fluoboric acid iodonium salt, aryl diazonium salt and Su Mao ferric salt.
5. The solvent-free high refractive index optical material according to claim 1, wherein the particle size of the inorganic nanoparticles is 1-50 nm.
6. The solventless high refractive index optical material of claim 1 wherein said cross-linking agent is one of pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol triacrylate, tri (2-hydroxyethyl) isocyanuric acid triacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.
7. A method for preparing the solvent-free high refractive index optical material according to claim 1, comprising the steps of:
and (3) adding the photoinitiator into the high refractive index dispersion liquid, fully mixing, and then adding the acrylic monomer, the cross-linking agent and the oligomer, and fully stirring to obtain the solvent-free high refractive index composition.
8. Use of the solventless high refractive index optical material of any one of claims 1-6 as an optically functional layer in an optoelectronic device comprising flash evaporation, ink jet printing, deposition, screen printing, spin coating or doctor blading of the solventless high refractive index optical material followed by uv irradiation.
CN202210562408.2A 2022-05-23 2022-05-23 Solvent-free high-refractive-index optical material and preparation method and application thereof Active CN115010849B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210562408.2A CN115010849B (en) 2022-05-23 2022-05-23 Solvent-free high-refractive-index optical material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210562408.2A CN115010849B (en) 2022-05-23 2022-05-23 Solvent-free high-refractive-index optical material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115010849A CN115010849A (en) 2022-09-06
CN115010849B true CN115010849B (en) 2023-07-18

Family

ID=83068283

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210562408.2A Active CN115010849B (en) 2022-05-23 2022-05-23 Solvent-free high-refractive-index optical material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115010849B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009102459A (en) * 2007-10-19 2009-05-14 Dai Ichi Kogyo Seiyaku Co Ltd Urethane (meth)acrylate composition and energy beam curing type resin composition
CN111303689A (en) * 2020-03-10 2020-06-19 宁波野山羊新材料科技有限公司 Non-solvent type photocuring composition, film layer and wire
CN112646185A (en) * 2020-11-30 2021-04-13 山东益丰生化环保股份有限公司 Modified polythiol with high refractive index and preparation method thereof
CN112680093A (en) * 2020-12-25 2021-04-20 上海绘兰材料科技有限公司 Solvent-free type photocuring resin composition and preparation method and application thereof
CN113214692A (en) * 2021-05-21 2021-08-06 武汉工程大学 High-refraction resin composition and preparation method thereof
CN113372744A (en) * 2021-05-21 2021-09-10 武汉工程大学 High-refractive-index acrylic optical material and preparation method and application thereof
CN114149543A (en) * 2021-12-16 2022-03-08 江苏富琪森新材料有限公司 Self-repairing acrylate material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009102459A (en) * 2007-10-19 2009-05-14 Dai Ichi Kogyo Seiyaku Co Ltd Urethane (meth)acrylate composition and energy beam curing type resin composition
CN111303689A (en) * 2020-03-10 2020-06-19 宁波野山羊新材料科技有限公司 Non-solvent type photocuring composition, film layer and wire
CN112646185A (en) * 2020-11-30 2021-04-13 山东益丰生化环保股份有限公司 Modified polythiol with high refractive index and preparation method thereof
CN112680093A (en) * 2020-12-25 2021-04-20 上海绘兰材料科技有限公司 Solvent-free type photocuring resin composition and preparation method and application thereof
CN113214692A (en) * 2021-05-21 2021-08-06 武汉工程大学 High-refraction resin composition and preparation method thereof
CN113372744A (en) * 2021-05-21 2021-09-10 武汉工程大学 High-refractive-index acrylic optical material and preparation method and application thereof
CN114149543A (en) * 2021-12-16 2022-03-08 江苏富琪森新材料有限公司 Self-repairing acrylate material and preparation method thereof

Also Published As

Publication number Publication date
CN115010849A (en) 2022-09-06

Similar Documents

Publication Publication Date Title
JP4859998B2 (en) Active energy ray-curable composition and use thereof
KR101235227B1 (en) Fluorine compound and active-energy-ray-curable resin composition comprising same
CN1286935C (en) Adhesive composition for optical component and binding film for optical component therewith
CN102504174A (en) Polyurethane acrylic acid ester and preparation method and application thereof
JP6094912B2 (en) Bicarbazole compound, photocurable composition, cured product thereof, curable composition for plastic lens, and plastic lens
CN105400251A (en) Hard coating composition, polarizing film using same and display
CN115010849B (en) Solvent-free high-refractive-index optical material and preparation method and application thereof
CN114921129B (en) Self-repairing high-refractive-index ink and preparation method and application thereof
CN103163570A (en) Optical film, backlight unit including the same, and optical display apparatus including the same
CN105418674A (en) High-refraction-rate resin and application thereof
WO2024088358A1 (en) High-flexibility ultraviolet curable ink and packaging layer thereof
WO2024007741A1 (en) Ink composition, packaging structure, and semiconductor device
CN101429353B (en) Activation energy radial curing paint for silicon rubber
CN108017730B (en) Photoresist composition, color filter and preparation method thereof
CN115260835A (en) High-refractive-index ink based on symmetric thioamide structure and preparation method thereof
JPH111633A (en) Thin optical film containing fluorine compound, method for forming the same and antireflection article
KR20150145414A (en) Oxime ester compound and a photopolymerizable composition comprising the same
CN111377817A (en) Resin and ink
CN111484859B (en) Additive and application thereof
CN113755092A (en) Preparation method of ultraviolet/sunlight curable fluorine-containing coating
TWI515255B (en) Curable resin and curable composition using the same
CN105254588A (en) High-refractive-index compound and application thereof
CN115895377A (en) Solvent type high-refractive-index composition and application thereof in OLED display device
CN114479651A (en) Self-repairable UV (ultraviolet) photocureable coating and preparation method thereof
CN115677502A (en) Acrylate monomer, UV curing glue, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant