WO2016015411A1 - 功能材料及其制备方法、树脂组合物、膜材、显示器件 - Google Patents

功能材料及其制备方法、树脂组合物、膜材、显示器件 Download PDF

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WO2016015411A1
WO2016015411A1 PCT/CN2014/091856 CN2014091856W WO2016015411A1 WO 2016015411 A1 WO2016015411 A1 WO 2016015411A1 CN 2014091856 W CN2014091856 W CN 2014091856W WO 2016015411 A1 WO2016015411 A1 WO 2016015411A1
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functional material
curable resin
resin composition
modified layer
oxide
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PCT/CN2014/091856
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English (en)
French (fr)
Inventor
杨久霞
白峰
刘建涛
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京东方科技集团股份有限公司
北京京东方光电科技有限公司
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Priority claimed from CN201410366767.6A external-priority patent/CN104292889B/zh
Application filed by 京东方科技集团股份有限公司, 北京京东方光电科技有限公司 filed Critical 京东方科技集团股份有限公司
Priority to US14/760,914 priority Critical patent/US9587121B2/en
Publication of WO2016015411A1 publication Critical patent/WO2016015411A1/zh

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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
    • 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
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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

Definitions

  • the present invention relates to the field of display technology, and in particular, to a functional material, a preparation method thereof, a curable resin composition, a film material, and a display device.
  • the invention aims to solve the problem that the existing display device is polluted, and provides a functional material which can play a health care role and is environmentally friendly, a preparation method thereof, a curable resin composition, a film material, and a display device.
  • the technical solution adopted to solve the technical problem of the present invention is a functional material comprising an inorganic powder having a modified layer on its surface, the inorganic powder comprising:
  • the modified layer is formed by the reaction of a dibasic anhydride and a diamine.
  • the ratio of the amount of the dibasic anhydride to the diamine used to form the modified layer is (0.85 to 1.05):1.
  • the ratio of the amount of the dibasic anhydride to the diamine used to form the modified layer is (0.92 to 1.05):1.
  • the dibasic anhydride used to form the modified layer contains at least one phenyl group; the diamine used to form the modified layer contains at least one phenyl or non-phenyl six-membered amine Carbon ring.
  • the dianhydride used to form the modified layer is selected from the group consisting of pyromellitic dianhydride, Any one of trimellitic anhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, and hexafluoro dianhydride;
  • the diamine used to form the modified layer is selected from the group consisting of 3-aminobenzylamine, 2 , 2'-difluoro-4,4'-(9-fluorenylene)diphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, hexahydro-m-xylylene Diamine, 1,4-bis(aminomethyl)cyclohexane, 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane, 2,2-bis(3-amino-4 -toluyl)hexafluoro
  • the inorganic powder has a particle diameter of from 1 to 5,000 nm.
  • the technical solution adopted to solve the technical problem of the present invention is a method for preparing the above functional material, which comprises:
  • the ratio of the mass of the inorganic powder to the mass of the substance formed by the reaction of the dibasic anhydride and the diamine is (20 to 1):1.
  • the heating is carried out in two steps, specifically: heating at a temperature of 35 to 70 ° C for 20 to 40 minutes; heating at a temperature of 70 to 100 ° C for 20 to 40 minutes.
  • the curable resin includes an acrylic resin and an epoxy resin; the curable resin composition further includes a coupling agent, a wetting leveling agent; in the case where the quality of the modified layer of the functional material is not calculated,
  • the mass percentage of each component in the curable resin composition is:
  • Acrylic resin 1 to 20%
  • Epoxy resin 1 to 20%
  • Coupling agent 1 to 10%
  • Wetting leveling agent 0.2 ⁇ 5%
  • Solvent 70 to 90%.
  • the curable resin includes an ethylenically unsaturated monomer; the photocurable agent, a wetting leveling agent is further included in the curable resin composition; and the quality of the modified layer of the functional material is not calculated
  • the mass percentage of each component in the curable resin composition is:
  • Vinyl unsaturated monomer 5 to 35%
  • Photoinitiator 0.01 to 1%
  • Wetting leveling agent 0.2 ⁇ 5%
  • the inorganic powder of the functional material in the curable resin composition has a mass percentage of 0.1 to 2.5%.
  • the inorganic powder of the functional material in the curable resin composition has a mass percentage of 0.1 to 2% without calculating the quality of the modified layer of the functional material.
  • the inorganic powder of the functional material in the curable resin composition has a mass percentage of 0.1 to 1.8% without calculating the quality of the modified layer of the functional material.
  • the mass percentage of a substance in the curable resin composition in the case where the quality of the modified layer of the functional material is not calculated means that the modified layer of the curable resin composition is other than the modified layer of the functional material.
  • the technical solution adopted to solve the technical problem of the present invention is a film comprising a transparent film layer formed by curing the above-mentioned curable resin composition.
  • the technical solution adopted to solve the technical problem of the present invention is a display device comprising a transparent film layer formed by curing the above-mentioned curable resin composition.
  • the functional material of the invention can emit far infrared rays and negative ions; the far infrared rays can be absorbed by the human body to resonate water molecules in the body, activate water molecules, enhance the intermolecular binding force, thereby activating biological macromolecules such as proteins, so that the living cells are at the highest vibration.
  • the inorganic powder surface of the functional material of the present invention has a modified layer which allows the inorganic powder to be well incorporated into the transparent film layer, and also enhances the ability of the inorganic powder to emit far infrared rays and negative ions.
  • the film material and display device of the present invention have a transparent film layer formed from the above-mentioned curable resin composition, so that it can continuously emit far infrared rays and negative ions during use, and is environmentally friendly.
  • FIG. 1 is a flow chart of a method of preparing a functional material according to an embodiment of the present invention.
  • This embodiment provides a functional material and a preparation method thereof.
  • the functional material includes an inorganic powder having a modified layer on the surface, and the inorganic powder includes alumina, magnesia, zinc oxide, zirconium oxide, silicon dioxide, titanium oxide, boron oxide, ferric oxide, calcium oxide, potassium oxide, Any one or more of sodium oxide and lithium oxide;
  • the modified layer is formed by the reaction of a dibasic anhydride and a diamine.
  • the inorganic powder has a particle diameter on the order of nanometers to micrometers, specifically, for example, 1 to 5000 nm, preferably 10 to 500 nm.
  • the particle size can be measured, for example, using a Malvern laser particle size analyzer.
  • the dibasic anhydride refers to a substance having at least two acid anhydride groups in a molecular structure
  • the diamine is a substance having at least two amine groups (or amino groups) in a molecular structure.
  • the dibasic anhydride contains, for example, at least one phenyl group, and is preferably any one of pyromellitic dianhydride, trimellitic anhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, and hexafluoro dianhydride.
  • pyromellitic dianhydride trimellitic anhydride
  • benzophenone dianhydride biphenyl dianhydride
  • diphenyl ether dianhydride diphenyl ether dianhydride
  • hexafluoro dianhydride hexafluoro dianhydride.
  • the diamine contains, for example, at least one phenyl or non-phenyl six-membered carbocyclic ring (for example, cyclohexane), which is preferably 3-aminobenzylamine, 2,2'-difluoro-4,4'- (9-fluorenylene) diphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, hexahydro-m-xylylenediamine, 1,4-bis(aminomethyl) Cyclohexane, 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2- Bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,7-diamin
  • the ratio of the amount of the dibasic anhydride to the diamine is, for example, (0.85 to 1.05):1; preferably at (0.92 to 1.05):1.
  • the modified layer formed by the reaction of the above dibasic anhydride and diamine can preferably improve the properties of the inorganic powder.
  • the functional material of the embodiment can emit far infrared rays and negative ions; the far infrared rays can be absorbed by the human body to resonate water molecules in the body, activate water molecules, enhance the intermolecular binding force, thereby activating biological macromolecules such as proteins, so that the living cells are at the highest level.
  • Vibration energy level; and far infrared heat can be transmitted to the deep part of the skin, so that the subcutaneous deep temperature rises, expands the capillaries, promotes blood circulation, strengthens the metabolism between tissues, enhances the ability of tissue regeneration, improves the body immunity, and regulates The abnormally excited state of the mind; and the negative ions have decomposition and oxidation effects on bacteria and organic matter, and can have the effect of sterilization and purification of ambient air quality; therefore, the functional materials of the embodiment can play a health care role and are environmentally friendly.
  • the preparation method of the above functional material comprises: uniformly mixing the inorganic powder, the dibasic anhydride, the diamine, the initiator, and the solvent; heating to react the dibasic anhydride with the diamine, and forming the modification on the surface of the inorganic powder. Sex layer.
  • the foregoing preparation method may include:
  • each of the raw materials is pulverized into a powder and then uniformly mixed in proportion, or the raw materials are uniformly mixed in proportion and then pulverized to obtain an inorganic powder.
  • the dispersing agent can be selected from the conventional dispersing agent such as BYK 161 produced by BYK of Germany, Solsperse 32500 and Solsperse 22000 produced by Lubrizol; the pulverization can be carried out by conventional methods such as ball milling and grinding; The method is therefore not described in detail here.
  • an initiator of 1/4 to 1/3 of the total amount and a diamine of 1/4 to 1/3 of the total amount are dissolved in a solvent for use.
  • the ratio of the mass of the inorganic powder to the mass of the substance formed by the reaction of the dibasic anhydride and the diamine is (20 to 1):1.
  • the amount of the dibasic anhydride and the diamine is determined as follows: It is assumed that the dibasic anhydride and the diamine can be completely reacted to obtain a product (actually a modified layer), if the mass of the product is 1
  • the quality of the inorganic powder is between 1 and 20; such an amount ensures that a modified layer of a suitable thickness is obtained on the inorganic powder.
  • an initiator is used to initiate the reaction, which is, for example, a nitrogen-based initiator, preferably azobisisobutyronitrile, 2,2'-bisazo-(2,4-dimethylvaleronitrile), azodi Any of dimethyl isobutyrate and azobisisovaleronitrile.
  • a nitrogen-based initiator preferably azobisisobutyronitrile, 2,2'-bisazo-(2,4-dimethylvaleronitrile), azodi Any of dimethyl isobutyrate and azobisisovaleronitrile.
  • the solvent may be selected from the group consisting of fatty alcohols, glycol ethers, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, monomethyl ether glycol ester, ⁇ -butyrolactone, and 3-ethyl ether ethyl propionate. , butyl carbitol, butyl card Conventional organic solvents such as phenolic acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, xylene, and isopropanol. Since the action of the solvent is only to disperse the respective substances, propylene glycol monomethyl ether acetate is uniformly used as a solvent in the process of specifically preparing the functional materials in the respective examples.
  • heating is started to carry out the reaction, which is carried out, for example, in two steps.
  • the method may further comprise: heating at a temperature of 35 to 70 ° C for 20 to 40 minutes; and then continuing to heat at a temperature of 70 to 100 ° C for 20 to 40 minutes.
  • a reaction between the dibasic anhydride and the diamine can be made to form a modified layer on the surface of the inorganic powder; wherein the stepwise heating is mainly to prevent the reaction from being too intense.
  • the reaction in this step is carried out, for example, under a nitrogen atmosphere, and stirring is maintained, for example, during the reaction.
  • the amount of the solvent in each step is determined by uniformly dispersing and dissolving the substance therein, and the amount of the initiator is based on the reaction, which can be adjusted by a person skilled in the art according to actual conditions, and will not be described in detail herein. .
  • the mass ratio (referred to as the total amount) of the inorganic powder, the initiator, and the solvent is 1: (0.25 to 0.4): (1 to 1.5), and in order to unify, the process of specifically preparing the functional material in each of the examples In the above, the mass ratio of the inorganic powder, the initiator, and the solvent was unified to 1:0.3:1.4.
  • reaction product is cooled to room temperature (about 10 to 30 ° C) with a refrigerated solvent.
  • dibasic anhydride, diamine, initiator, etc. can be dissolved in the solvent at one time; for example, heating can be only one step or the like.
  • heating can be only one step or the like.
  • the present embodiment also provides a curable resin composition
  • a curable resin composition comprising a curable resin, a solvent, and the above functional materials.
  • the curable resin composition can be cured to form a transparent film layer containing the above functional material, and the above functional material in the transparent film layer can continuously emit far infrared rays and negative ions, thereby improving the environment.
  • the mass percentage of the inorganic powder of the material is, for example, 0.1 to 2.5%, preferably 0.1 to 2%, more preferably 0.1 to 1.8%.
  • the functional material is The content of the inorganic powder is as described above.
  • the curable resin is a main material for forming a transparent film layer, and the curable resin composition is classified into two types of heat curing and ultraviolet curing depending on the type thereof.
  • the curable resin includes an acrylic resin and an epoxy resin; and further includes a coupling agent, a wetting leveling agent; in the case where the quality of the modified layer of the functional material is not calculated
  • the mass percentage of each component in the curable resin composition is:
  • Inorganic powder 0.1 to 2.5% (more preferably 0.1 to 2% or 0.1 to 1.8%);
  • Acrylic resin 1 to 20%
  • Epoxy resin 1 to 20%
  • Coupling agent 1 to 10%
  • Wetting leveling agent 0.2 ⁇ 5%
  • Solvent 70 to 90%.
  • the acrylic resin may be a methyl acrylate resin, an ethyl acrylate resin, a 2-methyl methacrylate resin, a 2-methyl methacrylate resin, a polyester acrylate, a urethane acrylate, an epoxy acrylate resin, or the like.
  • a substance of an acrylic group; the content thereof is, for example, 5 to 20%, preferably 5 to 15%.
  • the epoxy resin may be an aliphatic epoxy resin, a bisphenol A epoxy resin, a glycidyl ester epoxy resin, a heterocyclic epoxy resin, or the like; the content thereof is, for example, 5 to 20%, preferably 5 to 15 %.
  • the coupling agent is used to initiate a crosslinking reaction of the curable resin to cure it, which may be a silane coupling agent such as azidosilane, phenoxysilane, vinylsilane, aminosilane, epoxysilane, Mercaptosilane, methacryloxysilane, etc.; the content thereof is, for example, 1 to 8%, preferably 1 to 5%.
  • the wetting leveling agent is used to improve the leveling of the composition, and may be a silicone-based wetting leveling agent, a fluorocarbon-modified polyacrylate wetting leveling agent, an acrylic wetting leveling agent, and the like.
  • the solvent is used to dissolve and disperse other components to form a uniform, stable system, which may be a conventional organic solvent such as a ketone, an ester, an ether, an aliphatic hydrocarbon, a cycloalkane compound, an aromatic hydrocarbon or the like.
  • the curable resin is a vinyl unsaturated single And a photoinitiator, a wetting leveling agent; wherein the mass percentage of each component in the curable resin composition is calculated without calculating the quality of the modified layer of the functional material:
  • Inorganic powder 0.1 to 2.5% (more preferably 0.1 to 2% or 0.1 to 1.8%);
  • Vinyl unsaturated monomer 5 to 35%
  • Photoinitiator 0.01 to 1%
  • Wetting leveling agent 0.2 ⁇ 5%
  • the ethylenically unsaturated monomer means an unsaturated monomer substance containing a vinyl group, which may be vinyl chloride, styrene, methyl methacrylate, maleimide, butadiene, methyl acrylate, Epoxy acrylate, bisphenol A type epoxy methacrylate, etc.; and its content is, for example, 5 to 30%, preferably 5 to 25%.
  • the photoinitiator can initiate a crosslinking reaction upon irradiation with ultraviolet light to cure the ethylenically unsaturated monomer to form a transparent film layer; specifically, it can be: an ⁇ -amino ketone photoinitiator such as model Irgacure 907, Igracure 369 , Irgacure 1300 initiator; acylphosphine oxide photoinitiator, such as Irgacure 819, Irgacure 819DW, Irgacure 2010, Darocur TPO, Darocur 4265 initiator; ⁇ -hydroxyketone photoinitiator, such as model Darocur 1173, Irgacure 184 , Irgacure 2959, Irgacure 500, Irgacure 1000 initiator; benzoylformate photoinitiator, such as the type Darocur mbf, Irgacure 754 initiator.
  • the wetting leveling agent is used to improve the leveling of the composition, and may be a silicone-based wetting leveling agent, a fluorocarbon-modified polyacrylate wetting leveling agent, an acrylic wetting leveling agent, and the like.
  • the solvent is used to dissolve and disperse other components to form a uniform, stable system, which may be a conventional organic solvent such as a ketone, an ester, an ether, an aliphatic hydrocarbon, a cycloalkane compound, an aromatic hydrocarbon or the like.
  • the curable resin composition of the thermosetting type is continuously prepared by using the obtained functional material in accordance with the parameters in the following table, in which the components are uniformly mixed, without using a specific order of addition and mixing.
  • the acrylic resin was uniformly selected from the SB401 type acrylic resin produced by Sartomer Co., Ltd., and the epoxy resin was uniformly selected from the DEN 438 type phenolic epoxy tree produced by Dow Corporation.
  • the grease and coupling agent are selected by the type A186 (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), and the wetting leveling agent is uniformly selected as the wetting leveling agent of BYK 333.
  • the solvent was uniformly selected from propylene glycol methyl ether acetate (PMA).
  • the curable resin composition was cured to form a transparent film layer, specifically, the curable resin composition was coated on a substrate, and heat-cured at a temperature of 180 ° C for 20 minutes to form a transparent film layer having a thickness of 1 ⁇ m.
  • the resin composition forming the transparent film layer except for the functional material, it is a conventional component, and therefore, for the comparability of the results, other components other than the functional material are selected as a uniform substance.
  • the infrared specific radiance of the transparent film layer is tested according to the GB/T 7287-2008 standard, and the amount of negative ions generated by the transparent film is measured by an air negative ion measuring instrument (for example, KEC-900 type of Japan KEC Corporation), and then a spectrophotometer is used (for example, Japan Shimadzu UV-Vis spectrophotometer UV2550) tested its transmittance, the results are shown in the table below.
  • an air negative ion measuring instrument for example, KEC-900 type of Japan KEC Corporation
  • a spectrophotometer for example, Japan Shimadzu UV-Vis spectrophotometer UV2550 tested its transmittance
  • the functional materials of the respective examples were prepared in accordance with the parameters in the following tables (the parameters of the functional materials in the respective examples are the same as those in Table 1). Thereafter, the ultraviolet curable curable resin composition is prepared by using the functional material according to the parameters of the following table; wherein, in the preparation, the components are uniformly mixed, without using a specific feeding sequence and mixing method.
  • the vinyl unsaturated monomer is uniformly selected from dipentaerythritol pentaacrylate (DPHA), and the photoinitiator is uniformly selected as the photoinitiator of Irgacure 907, and the wetting leveling agent is uniformly selected as the model BYK 333.
  • the wet leveling agent and the solvent are uniformly selected from propylene glycol methyl ether acetate (PMA).
  • the curable resin composition is cured to form a transparent film layer, which is specifically coated with a curable resin composition on a substrate, and exposed to light at an ultraviolet light energy of 150 mJ/cm 2 , and then at a temperature of 200 ° C.
  • the film was further heated and cured for 15 minutes to form a transparent film layer having a thickness of 1 ⁇ m.
  • the resin composition forming the transparent film layer except for the functional material, it is a conventional component, and therefore, for the comparability of the results, other components other than the functional material are selected as a uniform substance.
  • the infrared specific radiance of the transparent film layer was tested in accordance with the GB/T 7287-2008 standard, and the amount of negative ions generated by the transparent film was measured by an air negative ion meter, and the transmittance was measured by a light intensity meter. The results are shown in the following table.
  • the transparent film layers of the embodiments have higher infrared radiance and negative ion concentration, and the transmittance is also higher, which proves that it does not affect the display, and at the same time, can generate far infrared rays and negative ions, thereby achieving Improve the role of the environment.
  • the inorganic powder surface of the functional material of the present embodiment has a modified layer which allows the inorganic powder to be well incorporated into the transparent film layer, and can also improve the ability of the inorganic powder to emit far infrared rays and negative ions.
  • the embodiment further provides a film comprising the cured by the above curable resin composition. Transparent film layer.
  • the above-mentioned curable resin composition can be applied onto a substrate by coating, transfer, printing, or the like, and then cured to form a transparent film layer, and the transparent film layer is removed and wound, Cutting or the like to form a film product such as a reel type film or a flat type film.
  • the thickness of the transparent film layer can be set as needed, but it can usually be between 0.005 ⁇ m and 1.5 ⁇ m.
  • the curable resin composition can be formed into a transparent film layer by heat curing or ultraviolet light curing; a specific curing method thereof is known and will not be described in detail herein.
  • the heating temperature in the heat curing is usually between 150 ° C and 250 ° C, and the heating time is between 5 min and 30 min; and in the ultraviolet curing, the ultraviolet light intensity is from 50 mJ/cm 2 to 200 mJ/cm 2 . between.
  • an adhesive layer provided on the transparent film layer to bond the transparent film layer at a desired position
  • a release film provided on the adhesive layer may be further included;
  • Known forms can be used and therefore will not be described in detail herein.
  • the present embodiment also provides a display device comprising a transparent film layer formed by curing the above-described curable resin composition.
  • the display device can be any type of display device such as a liquid crystal display device, an organic light emitting diode display device, a plasma display device, etc.; and it can be used for any of a television, a mobile phone, a computer display, a tablet computer, an e-book, a navigator, an ATM machine, etc. In the device that displays the function.
  • the transparent film layer may be disposed at any position of the display device (such as the inner side, the outer case, etc.); but preferably, since it is transparent, it does not affect the display, so it can be disposed on the light-emitting surface of the display device.
  • the outermost side in order to achieve the best effect of emitting far infrared rays and negative ions.
  • the transparent film layer can be formed into a film product as described above, and then the film is attached to the display device.
  • the surface of the display device may be used as a substrate, and a transparent film layer may be directly formed thereon.

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Abstract

本发明提供一种功能材料及其制备方法、可固化树脂组合物、膜材、显示器件，属于显示技术领域，其可解决现有显示器件存在污染的问题。本发明的功能材料包括表面带有改性层的无机粉末，无机粉末包括氧化铝、氧化镁、氧化锌、氧化锆、二氧化硅、二氧化钛、氧化硼、三氧化二铁、氧化钙、氧化钾、氧化钠、氧化锂中的任意一种或多种；改性层由二元酐和二元胺反应生成。本发明的可固化树脂组合物中含有上述功能材料。本发明的膜材和显示器件中包括由上述可固化树脂组合物固化形成的透明膜层。

Description

功能材料及其制备方法、树脂组合物、膜材、显示器件 技术领域
本发明涉及显示技术领域，尤其涉及一种功能材料及其制备方法、可固化树脂组合物、膜材、显示器件。
背景技术
随着技术的发展，在电视、电脑、手机等之中，各种显示器件获得了越来越广泛的应用。
但是，不论何种类型的显示器件(液晶显示器件、有机发光二极管显示器件、等离子显示器件等)，在使用中都会不可避免的产生一定的电磁辐射勿扰，对人体健康造成不良影响。
发明内容
本发明针对现有显示器件会产生污染的问题，提供一种可起到医疗保健作用且对环境友好的功能材料及其制备方法、可固化树脂组合物、膜材、显示器件。
解决本发明技术问题所采用的技术方案是一种功能材料，其包括表面带有改性层的无机粉末，所述无机粉末包括：
氧化铝、氧化镁、氧化锌、氧化锆、二氧化硅、二氧化钛、氧化硼、三氧化二铁、氧化钙、氧化钾、氧化钠、氧化锂中的任意一种或多种；
所述改性层由二元酐和二元胺反应生成。
例如，用于生成所述改性层的二元酐与二元胺的物质的量的比在(0.85～1.05)∶1。
进一步优选的是，用于生成所述改性层的二元酐与二元胺的物质的量的比在(0.92～1.05)∶1。
例如，所述用于生成所述改性层的二元酐中含有至少一个苯基；所述用于生成所述改性层的二元胺中含有至少一个苯基或非苯基的六元碳环。
进一步优选的是，用于生成所述改性层的二元酐选自均苯四甲酸二酐、 偏苯三酸酐、二苯酮二酐、联苯二酐、二苯醚二酐、六氟二酐中的任意一种；用于生成所述改性层的二元胺选自3-氨基苄胺、2,2'-二氟-4,4'-(9-亚芴基)二苯胺、2,2-双(3-氨基-4-羟苯基)六氟丙烷、六氢-间苯二甲基二胺、1,4-二(氨甲基)环己烷、2,2-双[4-(4-氨基苯氧基)苯]六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(4-氨基苯基)六氟丙烷、2,7-二氨基芴、间苯二甲胺、4,4'-亚甲基双(2-乙基-6-甲基苯胺)中的任意一种。
例如，所述无机粉末的粒径在1～5000nm。
解决本发明技术问题所采用的技术方案是一种制备上述功能材料的方法，其包括：
将所述无机粉末、二元酐、二元胺与引发剂、溶剂混合均匀；
加热使所述二元酐与二元胺反应，在无机粉末表面形成所述改性层。
例如，所述无机粉末的质量与二元酐、二元胺反应后生成的物质的质量的比为(20～1)∶1。
例如，所述加热分为两步进行，其具体为：在35～70℃的温度下加热20～40min；在70～100℃的温度下加热20～40min。
解决本发明技术问题所采用的技术方案是一种可固化树脂组合物，其包括：
可固化树脂；
溶剂；和
上述功能材料。
例如，所述可固化树脂包括丙烯酸树脂和环氧树脂；所述可固化树脂组合物还包括偶联剂、润湿流平剂；在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中各组分的质量百分含量为：
丙烯酸树脂：1～20％；
环氧树脂：1～20％；
偶联剂：1～10％；
润湿流平剂：0.2～5％；
溶剂：70～90％。
例如，所述可固化树脂包括乙烯基不饱和单体；所述可固化树脂组合物中还包括光引发剂、润湿流平剂；在不计算所述功能材料的改性层质量的情 况下，所述可固化树脂组合物中各组分的质量百分含量为：
乙烯基不饱和单体：5～35％；
光引发剂：0.01～1％；
润湿流平剂：0.2～5％；
溶剂：60～90％。
例如，在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中功能材料的无机粉末的质量百分含量在0.1～2.5％。
优选的是，在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中功能材料的无机粉末的质量百分含量在0.1～2％。
进一步优选的是，在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中功能材料的无机粉末的质量百分含量在0.1～1.8％。
其中，“在不计算功能材料的改性层质量的情况下，可固化树脂组合物中某物质的质量百分含量”是指以可固化树脂组合物中除功能材料的改性层之外的其余全部物质(功能材料的无机粉末、可固化树脂、润湿流平剂、溶剂、偶联剂、光引发剂等)的质量之和为100％时，某物质的质量百分含量。
解决本发明技术问题所采用的技术方案是一种膜材，其包括由上述可固化树脂组合物固化形成的透明膜层。
解决本发明技术问题所采用的技术方案是一种显示器件，其包括由上述可固化树脂组合物固化形成的透明膜层。
本发明的功能材料可发出远红外线和负离子；远红外线被人体吸收后可使体内水分子共振，活化水分子，增强分子间结合力，从而活化蛋白质等生物大分子，使生物体细胞处于最高振动能级；且远红外热量可传递到皮下较深的部分，使皮下深层温度上升，扩张毛细血管，促进血液循环，强化各组织之间的新陈代谢，增强组织再生能力，提高机体免疫力，调节精神异常兴奋状态；而负离子对细菌和有机物有分解和氧化作用，可起到杀菌消毒和净化环境空气质量的效果；因此，该功能材料可起到医疗保健作用，对环境友好。
本发明的功能材料的无机粉末表面具有改性层，该改性层可使无机粉末良好的融入透明膜层中，并且还可提高该无机粉末发射远红外线和负离子的能力。
本发明的膜材和显示器件具有由上述可固化树脂组合物生成的透明膜层，故其在使用过程中可持续发出远红外线和负离子，对环境友好。
附图说明
图1为本发明实施例的功能材料的制备方法的流程图。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图和具体实施方式对本发明作进一步详细描述。
本实施例提供一种功能材料及其制备方法。
该功能材料包括表面带有改性层的无机粉末，该无机粉末包括氧化铝、氧化镁、氧化锌、氧化锆、二氧化硅、二氧化钛、氧化硼、三氧化二铁、氧化钙、氧化钾、氧化钠、氧化锂中的任意一种或多种；且
所述改性层由二元酐和二元胺反应生成。
其中，无机粉末的粒径在纳米量级至微米量级，具体例如在1～5000nm，优选在10～500nm。粒径例如可采用马尔文激光粒度仪进行测量。
其中，二元酐是指分子结构中含有至少两个酸酐基团的物质；而二元胺是指分子结构中含有至少两个胺基(或氨基)的物质。
其中，二元酐中例如含有至少一个苯基，其优选为均苯四甲酸二酐、偏苯三酸酐、二苯酮二酐、联苯二酐、二苯醚二酐、六氟二酐中的任意一种。
其中，二元胺中例如含有至少一个苯基或非苯基的六元碳环(例如环己烷)，其优选为3-氨基苄胺、2,2'-二氟-4,4'-(9-亚芴基)二苯胺、2,2-双(3-氨基-4-羟苯基)六氟丙烷、六氢-间苯二甲基二胺、1,4-二(氨甲基)环己烷、2,2-双[4-(4-氨基苯氧基)苯]六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(4-氨基苯基)六氟丙烷、2,7-二氨基芴、间苯二甲胺、4,4'-亚甲基双(2-乙基-6-甲基苯胺)中的任意一种。
其中，二元酐与二元胺的物质的量的比例如为(0.85～1.05)∶1；优选在(0.92～1.05)∶1。
经研究发现，上述的二元酐和二元胺反应后生成的改性层可最好的改善无机粉末的性质。
本实施例的功能材料可发出远红外线和负离子；远红外线被人体吸收后可使体内水分子共振，活化水分子，增强分子间结合力，从而活化蛋白质等生物大分子，使生物体细胞处于最高振动能级；且远红外热量能传递到皮下较深的部分，使皮下深层温度上升，扩张毛细血管，促进血液循环，强化各组织之间的新陈代谢，增强组织再生能力，提高机体免疫力，调节精神异常兴奋状态；而负离子对细菌和有机物有分解和氧化作用，可起到杀菌消毒和净化环境空气质量的效果；因此，本实施例的功能材料可起到医疗保健作用，对环境友好。
上述功能材料的制备方法包括：将所述无机粉末、二元酐、二元胺与引发剂、溶剂混合均匀；加热使所述二元酐与二元胺反应，在无机粉末表面形成所述改性层。
具体的，如图1所示，上述制备方法可包括：
S01、在使用分散剂的情况下，将各原料分别粉碎为粉末后按比例混合均匀，或将各原料按比例混合均匀后再粉碎，得到无机粉末。
其中，分散剂可选用德国毕克公司生产的BYK 161、路博润公司生产的Solsperse 32500、Solsperse 22000等常规分散剂；粉碎可采用球磨、研磨等常规方式；由于得到无机粉末可采用已知的方法，故在此不再详细描述。
S02、将占总量1/4～1/3的引发剂及占总量1/4～1/3的二元胺溶解在溶剂中备用。
其中，无机粉末的质量与二元酐、二元胺反应后生成的物质的质量的比为(20～1)∶1。
也就是说，二元酐、二元胺的用量按照如下的方式确定：假设二元酐与二元胺可完全反应并得到生成物(实际为改性层)，若该生成物的质量为1，则无机粉末的质量就在1～20之间；这样的用量可保证在无机粉末上得到厚度合适的改性层。
其中，引发剂用于引发反应，其例如为氮类引发剂，优选为偶氮二异丁腈、2,2'-双偶氮-(2,4-二甲基戊腈)、偶氮二异丁酸二甲酯、偶氮二异戊腈中的任意一种。
其中，溶剂可选自脂肪醇、乙二醇醚、乙酸乙酯、甲乙酮、甲基异丁基酮、单甲基醚乙二醇酯、γ-丁内酯、丙酸-3-乙醚乙酯、丁基卡必醇、丁基卡 必醇醋酸酯、丙二醇单甲基醚、丙二醇单甲基醚醋酸酯、环己烷、二甲苯、异丙醇等常规的有机溶剂。由于溶剂的作用只是分散各物质，故在各实施例具体制备功能材料的过程中，统一采用丙二醇单甲基醚醋酸酯作溶剂。
S03、将无机粉末加入反应容器(如四口瓶)中，并开始搅拌、震荡、摇动等；之后加入二元酐、溶剂，以及剩余的引发剂、二元胺，溶解均匀。
S04、开始加热以进行反应，其例如分为两步进行，具体可包括：先在35～70℃的温度下加热20～40min；之后继续在70～100℃的温度下加热20～40min。
以上的加热过程中，可使二元酐与二元胺间发生反应，从而在无机粉末表面生成改性层；其中，之所以分步加热，主要是为了防止反应过于剧烈。
在反应过程中，逐渐将上述溶解有引发剂和二元胺的溶液逐滴加到四口瓶中；之所以这样加入，是为了防止反应过于剧烈。
其中，本步反应例如在氮气保护下进行，且在反应过程中例如一直保持搅拌。
其中，各步骤中溶剂的用量以能将其中的物质均匀的分散、溶解为准，而引发剂用量以能引发反应为准，这些可由本领域技术人员根据实际情况调整，在此不再详细描述。但通常而言，无机粉末、引发剂、溶剂的质量比(均指总量)为1∶(0.25～0.4)∶(1～1.5)，为了统一，故在各实施例具体制备功能材料的过程中，统一使无机粉末、引发剂、溶剂的质量比为1∶0.3∶1.4。
S05、反应结束后用经冷藏的溶剂使反应物冷却至室温(约10～30℃)。
S06、蒸干剩余溶剂或将粉末从中分离出来，得到带有改性层的无机粉末，即得到功能材料。
当然，应当理解，以上所述的制备方法还可进行许多变化，例如，二元酐、二元胺、引发剂等可一次都溶解在溶剂中；再如，加热也可只为一段等。总之，只要能使二元酐与二元胺反应并在无机粉末表面形成改性层即可。
本实施例还提供一种可固化树脂组合物，其中包括可固化树脂、溶剂、以及上述的功能材料。
可固化树脂组合物能固化形成透明膜层(其中含有上述功能材料)，而透明膜层中的上述功能材料可持续的发出远红外线和负离子，从而改善环境。
在不计算功能材料的改性层质量的情况下，可固化树脂组合物中功能材 料的无机粉末的质量百分含量例如在0.1～2.5％，优选在0.1～2％，进一步优选在0.1～1.8％。
也就是说，以可固化树脂组合物中除功能材料的改性层之外的其余全部物质(功能材料的无机粉末、可固化树脂、溶剂等)的质量之和为100％时，功能材料的无机粉末的含量如上所述。
在可固化树脂组合物中，可固化树脂是用于形成透明膜层的主要材料，依照其类型的不同，可固化树脂组合物分为热固化和紫外光固化两种类型。
在热固化型的可固化树脂组合物中，可固化树脂包括丙烯酸树脂和环氧树脂；且其中还包括偶联剂、润湿流平剂；在不计算功能材料的改性层质量的情况下，可固化树脂组合物中各组分的质量百分含量为：
无机粉末：0.1～2.5％(更优选在0.1～2％或0.1～1.8％)；
丙烯酸树脂：1～20％；
环氧树脂：1～20％；
偶联剂：1～10％；
润湿流平剂：0.2～5％；
溶剂：70～90％。
其中，丙烯酸树脂可以为丙烯酸甲酯树脂、丙烯酸乙酯树脂、2-甲基丙烯酸甲酯树脂、2-甲基丙烯酸乙酯树脂、聚酯丙烯酸酯、聚氨酯丙烯酸酯、环氧丙烯酸酯树脂等含有丙烯酸基团的物质；其含量例如在5～20％，优选5～15％。
其中，环氧树脂可为脂肪族环氧树脂、双酚A型环氧树脂、缩水甘油基酯类环氧树脂、杂环环氧树脂等；其含量例如在5～20％，优选5～15％。
其中，偶联剂用于引发可固化树脂的交联反应以使之固化，其可为硅烷偶联剂，例如叠氮硅烷、苯氧基硅烷、乙烯基硅烷、氨基硅烷、环氧基硅烷、巯基硅烷、甲基丙烯酰氧基硅烷等；其含量例如在1～8％，优选在1～5％。
润湿流平剂用于改善组合物的流平性，其可为有机硅类润湿流平剂、氟碳改性聚丙烯酸酯润湿流平剂、丙烯酸类润湿流平剂等。
溶剂用于将其他组分溶解、分散，以形成均匀、稳定的体系，其可为常规的有机溶剂，如酮、酯、醚、脂肪烃、环烷烃类化合物、芳香烃等。
在紫外光固化型的可固化树脂组合物中，可固化树脂为乙烯基不饱和单 体；且其中还包括光引发剂、润湿流平剂；在不计算所述功能材料的改性层质量的情况下，可固化树脂组合物中各组分的质量百分含量为：
无机粉末：0.1～2.5％(更优选在0.1～2％或0.1～1.8％)；
乙烯基不饱和单体：5～35％；
光引发剂：0.01～1％；
润湿流平剂：0.2～5％；
溶剂：60～90％。
其中，乙烯基不饱和单体是指含有乙烯基团的不饱和单体物质，其可为氯乙烯、苯乙烯、甲基丙烯酸甲酯、马来酰亚胺、丁二烯、丙烯酸甲酯、环氧丙烯酸酯、双酚A型环氧丙烯酸甲酯等；且其含量例如在5～30％，优选5～25％。
光引发剂可在被紫外光照射时引发交联反应，使乙烯基不饱和单体固化形成透明膜层；其具体可为：α-胺基酮类光引发剂，如型号Irgacure 907，Igracure 369、Irgacure 1300的引发剂；酰基膦氧化物光引发剂，如型号Irgacure819、Irgacure 819DW、Irgacure 2010、Darocur TPO、Darocur 4265的引发剂；α-羟基酮类光引发剂，如型号Darocur 1173、Irgacure 184、Irgacure 2959、Irgacure 500、Irgacure 1000的引发剂；苯酰甲酸酯类光引发剂，如型号Darocur mbf、Irgacure754的引发剂。
润湿流平剂用于改善组合物的流平性，其可为有机硅类润湿流平剂、氟碳改性聚丙烯酸酯润湿流平剂、丙烯酸类润湿流平剂等。
溶剂用于将其他组分溶解、分散，以形成均匀、稳定的体系，其可为常规的有机溶剂，如酮、酯、醚、脂肪烃、环烷烃类化合物、芳香烃等。
当然，应当理解，在以上的可固化树脂组合物中，还可含有其他的物质，例如其他类型的可固化树脂，其他添加剂(如消泡剂等)，其他的引发剂等。
按照上述的制备方法，依照以下表格中的参数制备各实施例的功能材料。
之后，用所得功能材料继续按照以下表格中的参数制备热固化型的可固化树脂组合物，其制备中只要将各组分混合均匀即可，而不必采用特定的加料顺序及混合方法。
在各实施例中，丙烯酸树脂统一选用Sartomer公司生产的SB401型丙烯酸树脂，环氧树脂统一选用美国陶氏公司生产的DEN 438型酚醛环氧树 脂，偶联剂统一选用型号为A186的(2-(3,4-环氧环己基)乙基三甲氧基硅烷)，润湿流平剂统一选用型号为BYK 333的润湿流平剂，溶剂统一选用丙二醇甲醚醋酸酯(PMA)。
之后，用可固化树脂组合物固化形成透明膜层，其具体为将可固化树脂组合物涂布在基底上，并在180℃的温度下加热固化20min，形成厚度为1μm的透明膜层。
其中，在形成透明膜层的树脂组合物中，除功能材料外均为常规组分，故在此为了结果的可比性，除功能材料外的其他的组分选用了统一的物质。
之后，按照GB/T 7287-2008标准测试透明膜层的红外线比辐射率，并用空气负离子测定仪(例如日本KEC公司的KEC-900型)测量其产生的负离子数量，再用分光光度计(例如日本岛津紫外可见分光光度计UV2550)测试其透过率，结果如下表所示。
表1、功能材料及热固化型的可固化树脂组合物的相关参数(含量单位均为质量份数)
Figure PCTCN2014091856-appb-000001
Figure PCTCN2014091856-appb-000002
按照上述的制备方法，依照以下表格中的参数制备各实施例的功能材料(各实施例中功能材料的参数与表1中的相同)。之后用该功能材料依照以下表格的参数制备紫外光固化型的可固化树脂组合物；其中，制备中只要将各组分混合均匀即可，而不必采用特定的加料顺序及混合方法。
在各实施例中，乙烯基不饱和单体统一选用二季戊四醇五丙烯酸酯(DPHA)，光引发剂统一选用型号为Irgacure 907的光引发剂、润湿流平剂统一选用型号为BYK 333的润湿流平剂、溶剂统一选用丙二醇甲醚醋酸酯(PMA)。
之后，用可固化树脂组合物固化形成透明膜层，其具体为将可固化树脂组合物涂布在基底上，并在150mJ/cm2的紫外光能量下照射下曝光，然后在200℃的温度下继续加热固化15min，形成厚度为1μm的透明膜层。
其中，在形成透明膜层的树脂组合物中，除功能材料外均为常规组分，故在此为了结果的可比性，除功能材料外的其他的组分选用了统一的物质。
之后，按照GB/T 7287-2008标准测试透明膜层的红外线比辐射率，并用空气负离子测定仪测量其产生的负离子数量，再用光强度计测试其透过率，结果如下表所示。
表2、功能材料及紫外光固化型的可固化树脂组合物的相关参数(含量单位均为质量份数)
Figure PCTCN2014091856-appb-000003
Figure PCTCN2014091856-appb-000004
可见，各实施例的透明膜层均具有较高的红外线比辐射率和负离子浓度，且透过率也较高，证明其不会对显示造成影响，且同时可产生远红外线和负离子，从而达到改善环境的作用。
本实施例的功能材料的无机粉末表面具有改性层，该改性层可使无机粉末良好的融入透明膜层中，并且还可提高该无机粉末发射远红外线和负离子的能力。
本实施例还提供一种膜材，其包括由上述可固化树脂组合物固化形成的 透明膜层。
也就是说，可将上述的可固化树脂组合物通过涂布、转印、印刷等方式施加在基底上，之后使其固化形成透明膜层，并将该透明膜层取下，进行卷绕、切割等操作，从而形成卷轴型膜材、平板型膜材等膜材产品。
其中，透明膜层的厚度可根据需要设定，但通常可在0.005μm至1.5μm之间。如前所述，可固化树脂组合物可通过热固化或紫外光固化的方式形成透明膜层；其具体的固化方法是已知的，在此不再详细限定。但通常而言，热固化中的加热温度通常在150℃至250℃之间，加热时间在5min至30min之间；而紫外光固化中，紫外光强度在50mJ/cm2至200mJ/cm2之间。
在膜材中，还可包括设于透明膜层上的粘结层(以便将透明膜层粘结在所需位置)，设于粘结层上的离型膜等其他结构；由于这些其他结构可采用已知的形式，故在此不再详细描述。
本实施例还提供一种显示器件，其包括由上述可固化树脂组合物固化形成的透明膜层。
该显示器件可为液晶显示器件、有机发光二极管显示器件、等离子显示器件等任何类型的显示器件；且其可用于电视、手机、电脑显示器、平板电脑、电子书、导航仪、ATM机等任何具有显示功能的装置中。
透明膜层可设于显示器件的任何位置处(如内侧、外壳上等)；但优选的，由于其是透明的，不会对显示造成影响，故可将其设于显示器件的出光面的最外侧，以便达到最好的发射远红外线和负离子的效果。
具体的，透明膜层可如前所述先形成膜材产品，之后将膜材贴附在显示器件上。或者，也可用显示器件的表面为基底，而直接将透明膜层形成在其上。
可以理解的是，以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。
本申请要求于2014年7月29日递交的中国专利申请第201410366767.6号的优先权，在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。

Claims (17)

  1. 一种功能材料，其包括表面带有改性层的无机粉末，所述无机粉末包括：
    氧化铝、氧化镁、氧化锌、氧化锆、二氧化硅、二氧化钛、氧化硼、三氧化二铁、氧化钙、氧化钾、氧化钠、氧化锂中的任意一种或多种；
    所述改性层由二元酐和二元胺反应生成。
  2. 根据权利要求1所述的功能材料，其中，
    用于生成所述改性层的二元酐与二元胺的物质的量的比在(0.85～1.05)∶1。
  3. 根据权利要求2所述的功能材料，其中，
    用于生成所述改性层的二元酐与二元胺的物质的量的比在(0.92～1.05)∶1。
  4. 根据权利要求1所述的功能材料，其中，
    所述用于生成所述改性层的二元酐中含有至少一个苯基；
    所述用于生成所述改性层的二元胺中含有至少一个苯基或非苯基的六元碳环。
  5. 根据权利要求4所述的功能材料，其中，
    用于生成所述改性层的二元酐选自均苯四甲酸二酐、偏苯三酸酐、二苯酮二酐、联苯二酐、二苯醚二酐、六氟二酐中的任意一种；
    用于生成所述改性层的二元胺选自3-氨基苄胺、2,2'-二氟-4,4'-(9-亚芴基)二苯胺、2,2-双(3-氨基-4-羟苯基)六氟丙烷、六氢-间苯二甲基二胺、1,4-二(氨甲基)环己烷、2,2-双[4-(4-氨基苯氧基)苯]六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(4-氨基苯基)六氟丙烷、2,7-二氨基芴、间苯二甲胺、4,4'-亚甲基双(2-乙基-6-甲基苯胺)中的任意一种。
  6. 根据权利要求1至5中任意一项所述的功能材料，其中，
    所述无机粉末的粒径在1～5000nm。
  7. 一种制备权利要求1至6中任意一项所述的功能材料的方法，所述制备方法包括：
    将所述无机粉末、二元酐、二元胺与引发剂、溶剂混合均匀；
    加热使所述二元酐与二元胺反应，在无机粉末表面形成所述改性层。
  8. 根据权利要求7所述的功能材料的制备方法，其中，
    所述无机粉末的质量与二元酐、二元胺反应后生成的物质的质量的比为(20～1)∶1。
  9. 根据权利要求7所述的功能材料的制备方法，其中，所述加热分为两步进行，其具体为：
    在35～70℃的温度下加热20～40min；
    在70～100℃的温度下加热20～40min。
  10. 一种可固化树脂组合物，其包括：
    可固化树脂；
    溶剂；和
    权利要求1至6中任意一项所述的功能材料。
  11. 根据权利要求10所述的可固化树脂组合物，其中，所述可固化树脂包括丙烯酸树脂和环氧树脂；所述可固化树脂组合物还包括偶联剂、润湿流平剂；在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中各组分的质量百分含量为：
    丙烯酸树脂：1～20％；
    环氧树脂：1～20％；
    偶联剂：1～10％；
    润湿流平剂：0.2～5％；
    溶剂：70～90％。
  12. 根据权利要求10所述的可固化树脂组合物，其中，所述可固化树脂 包括乙烯基不饱和单体；所述可固化树脂组合物中还包括光引发剂、润湿流平剂；在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中各组分的质量百分含量为：
    乙烯基不饱和单体：5～35％；
    光引发剂：0.01～1％；
    润湿流平剂：0.2～5％；
    溶剂：60～90％。
  13. 根据权利要求10至12中任意一项所述的可固化树脂组合物，其中，
    在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中功能材料的无机粉末的质量百分含量在0.1～2.5％。
  14. 根据权利要求13所述的可固化树脂组合物，其中，
    在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中功能材料的无机粉末的质量百分含量在0.1～2％。
  15. 根据权利要求14所述的可固化树脂组合物，其中，
    在不计算所述功能材料的改性层质量的情况下，所述可固化树脂组合物中功能材料的无机粉末的质量百分含量在0.1～1.8％。
  16. 一种膜材，其特征在于，包括：
    由权利要求10至15中任意一项所述的可固化树脂组合物固化形成的透明膜层。
  17. 一种显示器件，其包括：
    由权利要求10至15中任意一项所述的可固化树脂组合物固化形成的透明膜层。
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