CN113912792B - Preparation method and application of high-refractive-index nano zirconia composite resin - Google Patents
Preparation method and application of high-refractive-index nano zirconia composite resin Download PDFInfo
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- CN113912792B CN113912792B CN202111311083.2A CN202111311083A CN113912792B CN 113912792 B CN113912792 B CN 113912792B CN 202111311083 A CN202111311083 A CN 202111311083A CN 113912792 B CN113912792 B CN 113912792B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000000805 composite resin Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims abstract description 49
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 acrylic ester Chemical class 0.000 claims abstract description 7
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 3
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 3
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 230000029226 lipidation Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Classifications
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- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Nonlinear Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a high refractive index nano zirconia composite resin, which comprises the following steps: (1) preparing nano tetragonal zirconia powder by a hydrothermal method; (2) Cationic surfactant is added in the modification process of tetragonal zirconia, and Ca (OH) 2 The surface of tetragonal zirconia particles absorbs hydroxyl to the greatest extent under alkaline environment, acrylic acid is added to neutralize part of Ca (OH) 2 Simultaneously, generating a lipidation reaction with hydroxyl groups on the surfaces of tetragonal zirconia particles under the catalysis of concentrated sulfuric acid; (3) Dispersing the prepared modified tetragonal zirconia powder into an acrylic ester monomer to obtain the high-refractive-index nano zirconia composite resin material, wherein the refractive index is as high as 1.68. The high refractive index nano zirconia composite resin material is used for preparing the brightness enhancement film in the liquid crystal backlight module, so that the light condensation degree of the prism on the brightness enhancement film is improved, and the brightness loss is reduced.
Description
Technical Field
The invention relates to the technical field of optical films, in particular to a preparation method and application of a high-refractive-index nano zirconia composite resin.
Background
Liquid crystal display panels have been commonly used in display screens of computers, mobile phones, televisions, navigators, digital cameras and some instruments. Since the liquid crystal panel itself does not emit light, the backlight module, which is one of the key components of the liquid crystal display panel, plays a role in providing sufficient brightness and uniform light. The basic constitution of the backlight module except the light source comprises from bottom to top: reflective films, light guide plates, diffusion films, and brightness enhancement films, etc. The backlight source passes through the brightness enhancement film with the prism structure from the lower part, and then condenses light to enter the liquid crystal module, and at the moment, the optical refractive index directly influences whether the path of light rays can enter the target area more vertically.
The brightness enhancement film is generally based on an acrylate resin, and the optical refractive index is best represented by about 1.6. When the refractive index is lower, the light is more likely to deflect, so that the polarizing plates between the backlight modules reflect, brightness loss is generated, and backlight benefit is reduced.
At present, increasing the refractive index of an optical film has become the most important research topic for a brightness enhancement film, but inorganic nano-oxide has a high refractive index, but the dispersibility of inorganic nano-oxide particles in acrylate resin is poor, and it is difficult to make a brightness enhancement prism structure (brightness enhancement film).
Disclosure of Invention
In view of the above-mentioned shortcomings, one of the purposes of the present invention is to provide a high refractive index nano zirconia composite resin material, in which the modified nano zirconia can be well dispersed in acrylate monomers, and the refractive index is as high as 1.68.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows: the preparation method of the high refractive index nano zirconia composite resin comprises the following steps:
(1) Taking ZrOCl 2 ·8H 2 Dissolving O in deionized water to obtain zirconium oxychloride solution, adding NaOH to adjust pH to 10, adding glycerol, stirring, placing in a hydrothermal reaction kettle, reacting at 180deg.C for 24 hr, cooling to room temperature, centrifuging, taking out precipitate, and adding H 3 PO 4 Adjusting the pH value to 7, adding 25wt.% of ethanol, standing for 16 hours, and carrying out centrifugal separation, water washing, ethanol washing and powder spraying drying to obtain tetragonal zirconia powder; (2) 75 to 100 weight portions of tetragonal zirconia powder, 0.1 to 0.2 weight portion of cationic surfactant and 800 to 900 weight portions of deionized water are subjected to ultrasonic vibration for 1 hour,adding 15-20 parts by weight of Ca (OH) 2 Soaking for 3-6h after stirring uniformly, carrying out ultrasonic vibration for 30min at 60-80 ℃, taking out precipitate after centrifugal separation, adding 20-30 parts by weight of acrylic acid, carrying out ultrasonic vibration for 30min, continuously adding 0.01-0.05 part by weight of concentrated sulfuric acid, stirring and reacting for 4-6h at 45-50 ℃, washing with water, washing with ethanol, carrying out centrifugal separation, and carrying out powder spraying and drying to obtain modified tetragonal zirconia powder;
(3) And (3) dispersing the modified tetragonal zirconia powder prepared in the step (2) into an acrylic ester monomer to obtain the high-refractive-index nano zirconia composite resin material.
Further, the concentration of the zirconium oxychloride solution in the step (1) is 0.5-2mol/L.
Further, the glycerol added in the step (1) is ZrOCl 2 ·8H 2 0.5-1wt.% of O mass.
Further, the cationic surfactant in the step (2) is one of octadecyl trimethyl ammonium chloride, benzalkonium chloride and tributyl methyl ammonium chloride.
Further, the particle size of the tetragonal zirconia powder in the step (1) is 4-8nm.
Further, the particle size of the modified tetragonal zirconia powder in the step (2) is 8-15nm.
Further, the mass ratio of the modified tetragonal zirconia powder to the acrylic ester monomer in the step (3) is 26-69%.
Further, the acrylic ester monomer is one of an ethyl acrylate monomer, an ethyl methacrylate monomer and a 2-hydroxyethyl acrylate monomer.
The second object of the present invention is to provide an application of the high refractive index nano zirconia composite resin material, wherein the high refractive index nano zirconia composite resin material is used for preparing a brightness enhancement film in a liquid crystal backlight module.
The beneficial effects of the invention are as follows:
(1) Tetragonal zirconia produced by hydrothermal method has hydroxyl group attracting capacity and is characterized by Ca (OH) 2 In the alkaline environment, a cationic surfactant is adopted to improve the adsorption capacity of hydroxyl groups on the surfaces of the tetragonal zirconia particlesForce.
(2) Adding acrylic acid, partially neutralizing Ca (OH) 2 The generated calcium salt is contained in water and reacts with hydroxyl groups on the surface of tetragonal zirconia particles to generate lipidation reaction under the catalysis of concentrated sulfuric acid.
(3) The modified tetragonal zirconia powder can be well dispersed into acrylate monomers, and the refractive index can reach 1.68 at the highest.
(4) The high refractive index nano zirconia composite resin material is used for preparing the brightness enhancement film in the liquid crystal backlight module, so that the light condensation degree of the prism on the brightness enhancement film is improved, and the brightness loss is reduced.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The reagents or apparatus used in the present invention are conventional products commercially available without identifying the manufacturer.
Example 1
The preparation method of the high refractive index nano zirconia composite resin comprises the following steps:
(1) Taking ZrOCl 2 ·8H 2 Dissolving O in deionized water to obtain 0.5mol/L zirconium oxychloride solution, adding NaOH to regulate pH value to 10, adding glycerol with ZrOCl 2 ·8H 2 0.5wt.% of O, stirring, placing in a hydrothermal reaction kettle, reacting at 180deg.C for 24 hr, cooling to room temperature, centrifuging, taking out precipitate, and adding H 3 PO 4 Adjusting the pH value to 7, adding 25wt.% ethanol, standing for 16 hours, and carrying out centrifugal separation, water washing, ethanol washing and powder spraying drying to obtain tetragonal zirconia powder with the particle size of 4 nm;
(2) 75 parts by weight of tetragonal zirconia powder, 0.1 part by weight of octadecyl trimethyl ammonium chloride and 800 parts by weight of deionized water are subjected to ultrasonic vibration for 1h, and 15 parts by weight of Ca (OH) is added 2 Stirring, soaking for 3 hr, ultrasonic oscillating at 60deg.C for 30min, centrifuging, and collectingAdding 20 parts by weight of acrylic acid into the precipitate, carrying out ultrasonic vibration for 30min, continuously adding 0.01 part by weight of concentrated sulfuric acid, stirring and reacting for 6h at 45 ℃, washing with water, washing with ethanol, centrifugally separating, spraying powder and drying to obtain modified tetragonal zirconia powder with the particle size of 10 nm;
(3) And (3) dispersing 8.10g of the modified tetragonal zirconia powder prepared in the step (2) into 30mL of ethyl acrylate monomer to obtain the high-refractive-index nano zirconia composite resin material.
Example 2
Example 2 is different from example 1 in that 14.06g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of ethyl acrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 3
Example 3 is different from example 1 in that 17.24g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of ethyl acrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 4
Example 4 is different from example 1 in that 18.64g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of ethyl acrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 5
The preparation method of the high refractive index nano zirconia composite resin comprises the following steps:
(1) Taking ZrOCl 2 ·8H 2 Dissolving O in deionized water to obtain 2mol/L zirconium oxychloride solution, adding NaOH to regulate pH value to 10, adding glycerol with the addition amount of ZrOCl 2 ·8H 2 1wt.% of O mass, stirring uniformly, placing into a hydrothermal reaction kettle, reacting at 180 ℃ for 24H, cooling to room temperature, centrifuging, taking out precipitate, and adding H 3 PO 4 Adjusting the pH value to 7, adding 25wt.% ethanol, standing for 16 hours, and carrying out centrifugal separation, water washing, ethanol washing and powder spraying drying to obtain tetragonal zirconia powder with the particle size of 8 nm;
(2) 85 parts by weight of tetragonal zirconia powder, 015 parts by weight of benzalkonium chloride and 900 parts by weight of deionized water, vibrating for 1 hour by ultrasonic wave, and adding 18 parts by weight of Ca (OH) 2 Stirring uniformly, soaking for 6h, carrying out ultrasonic vibration at 60 ℃ for 30min, taking out precipitate after centrifugal separation, adding 25 parts by weight of acrylic acid, carrying out ultrasonic vibration for 30min, continuously adding 0.03 part by weight of concentrated sulfuric acid, stirring at 50 ℃ for reaction for 5h, washing with water, washing with ethanol, carrying out centrifugal separation, and carrying out powder spraying and drying to obtain modified tetragonal zirconia powder with the particle size of 8 nm;
(3) And (3) dispersing 8.20g of the modified tetragonal zirconia powder prepared in the step (2) into 30mL of ethyl methacrylate monomer to obtain the high-refractive-index nano zirconia composite resin material.
Example 6
Example 6 is different from example 5 in that 14.15g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of ethyl methacrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 7
Example 7 is different from example 5 in that 17.28g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of ethyl methacrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 8
Example 8 differs from example 5 in that 18.66g of the modified tetragonal zirconia powder obtained in step (2) was dispersed in 30mL of ethyl methacrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 9
The preparation method of the high refractive index nano zirconia composite resin comprises the following steps:
(1) Taking ZrOCl 2 ·8H 2 Dissolving O in deionized water to obtain 1.5mol/L zirconium oxychloride solution, adding NaOH to regulate pH value to 10, adding glycerol with ZrOCl 2 ·8H 2 1wt.% of O mass, stirring uniformly, placing into a hydrothermal reaction kettle, reacting at 180 ℃ for 24H, cooling to room temperature, centrifuging, taking out precipitate, and adding H 3 PO 4 The pH value is adjusted to be 7,adding 25wt.% ethanol, standing for 16 hours, centrifuging, washing with water, washing with ethanol, spraying powder, and drying to obtain tetragonal zirconia powder with particle diameter of 6 nm;
(2) 100 parts by weight of tetragonal zirconia powder, 0.2 part by weight of tributyl methyl ammonium chloride and 900 parts by weight of deionized water are subjected to ultrasonic vibration for 1h, and 20 parts by weight of Ca (OH) is added 2 Stirring uniformly, soaking for 5h, carrying out ultrasonic vibration at 80 ℃ for 30min, taking out precipitate after centrifugal separation, adding 30 parts by weight of acrylic acid, carrying out ultrasonic vibration for 30min, continuously adding 0.05 part by weight of concentrated sulfuric acid, stirring at 50 ℃ for reaction for 4h, washing with water, washing with ethanol, carrying out centrifugal separation, spraying powder, and drying to obtain modified tetragonal zirconia powder with the particle size of 15 nm;
(3) And (3) dispersing 8.58g of the modified tetragonal zirconia powder prepared in the step (2) into 30mL of 2-hydroxyethyl acrylate monomer to obtain the high-refractive-index nano zirconia composite resin material.
Example 10
Example 10 differs from example 9 in that 15.43g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of 2-hydroxyethyl acrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 11
Example 11 differs from example 9 in that 19.28g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of 2-hydroxyethyl acrylate monomer to obtain a high refractive index nano zirconia composite resin material.
Example 12
Example 12 differs from example 9 in that 21.03g of the modified tetragonal zirconia powder obtained in the step (2) was dispersed in 30mL of 2-hydroxyethyl acrylate monomer to obtain a high refractive index nano zirconia composite resin material.
The nano zirconia composite resin materials prepared in examples 1 to 12 and the acrylate monomer in the examples were subjected to test analysis of refractive index by using an optical refractive index (Abbe refractometer), and the test results are shown in Table 1 below:
TABLE 1
The tetragonal zirconia produced by the hydrothermal method has the capability of attracting hydroxyl, and can be used as a catalyst in Ca (OH) 2 Under alkaline environment, cationic surfactant is adopted to increase the hydroxyl adsorption capacity of the surface of tetragonal zirconia particles, acrylic acid is added to partially neutralize Ca (OH) 2 The generated calcium salt is contained in water and also reacts with hydroxyl groups on the surfaces of tetragonal zirconia particles to generate lipidation reaction under the catalysis of concentrated sulfuric acid.
The modified tetragonal zirconia powder can be well dispersed into acrylate monomers, and the refractive index can reach 1.68 at the highest.
The high refractive index nano zirconia composite resin material prepared by the invention is used for preparing the brightness enhancement film in the liquid crystal backlight module, so that the light condensation degree of the prism on the brightness enhancement film can be improved, and the brightness loss is reduced.
Those skilled in the art can also make appropriate changes and modifications to the above-described embodiments in light of the above disclosure. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (7)
1. A high refractive index nano zirconia composite resin is characterized in that: the preparation method comprises the following steps: (1) Taking ZrOCl 2 ·8H 2 Dissolving O in deionized water to obtain zirconium oxychloride solution, adding NaOH to adjust pH to 10, adding glycerol, stirring, placing in a hydrothermal reaction kettle, reacting at 180deg.C for 24 hr, cooling to room temperature, centrifuging, taking out precipitate, and adding H 3 PO 4 Modulation of pThe H value is 7, 25wt.% of ethanol is added and the mixture is placed for 16 hours, and the tetragonal zirconia powder is obtained through centrifugal separation, water washing, ethanol washing and powder spraying drying; (2) Adding 75-100 weight parts of tetragonal zirconia powder, 0.1-0.2 weight parts of cationic surfactant and 800-900 weight parts of deionized water into the mixture, performing ultrasonic vibration for 1h, and adding 15-20 weight parts of Ca (OH) 2 Soaking for 3-6h after stirring uniformly, carrying out ultrasonic vibration for 30min at 60-80 ℃, taking out precipitate after centrifugal separation, adding 20-30 parts by weight of acrylic acid, carrying out ultrasonic vibration for 30min, continuously adding 0.01-0.05 part by weight of concentrated sulfuric acid, stirring and reacting for 4-6h at 45-50 ℃, washing with water, washing with ethanol, carrying out centrifugal separation, and carrying out powder spraying and drying to obtain modified tetragonal zirconia powder;
(3) Dispersing the modified tetragonal zirconia powder prepared in the step (2) into an acrylic ester monomer to obtain a high-refractive-index nano zirconia composite resin material;
the mass ratio of the modified tetragonal zirconia powder to the acrylic ester monomer is 26-69%;
the acrylic ester monomer is one of an ethyl acrylate monomer, an ethyl methacrylate monomer and a 2-hydroxyethyl acrylate monomer.
2. The high refractive index nano zirconia composite resin according to claim 1, wherein: the concentration of the zirconium oxychloride solution in the step (1) is 0.5-2mol/L.
3. The high refractive index nano zirconia composite resin according to claim 1, wherein: the glycerol added in the step (1) is ZrOCl 2 ·8H 2 0.5-1wt.% of O mass.
4. The high refractive index nano zirconia composite resin according to claim 1, wherein: the cationic surfactant in the step (2) is one of octadecyl trimethyl ammonium chloride, benzalkonium chloride and tributyl methyl ammonium chloride.
5. The high refractive index nano zirconia composite resin according to claim 1, wherein: the grain size of the tetragonal zirconia powder in the step (1) is 4-8nm.
6. The high refractive index nano zirconia composite resin according to claim 1, wherein: the particle size of the modified tetragonal zirconia powder in the step (2) is 8-15nm.
7. Use of the high refractive index nano zirconia composite resin material according to any one of claims 1 to 6, characterized in that: the high refractive index nano zirconia composite resin material is used for preparing a brightness enhancement film in a liquid crystal backlight module.
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| CN202111311083.2A CN113912792B (en) | 2021-11-08 | 2021-11-08 | Preparation method and application of high-refractive-index nano zirconia composite resin |
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| CN202111311083.2A CN113912792B (en) | 2021-11-08 | 2021-11-08 | Preparation method and application of high-refractive-index nano zirconia composite resin |
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| CN113912792B true CN113912792B (en) | 2023-12-15 |
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