CN115785712A - High-refractive-index blue-light-proof modified epoxy acrylate material and optical filter - Google Patents
High-refractive-index blue-light-proof modified epoxy acrylate material and optical filter Download PDFInfo
- Publication number
- CN115785712A CN115785712A CN202211609725.1A CN202211609725A CN115785712A CN 115785712 A CN115785712 A CN 115785712A CN 202211609725 A CN202211609725 A CN 202211609725A CN 115785712 A CN115785712 A CN 115785712A
- Authority
- CN
- China
- Prior art keywords
- light
- modified epoxy
- blue
- epoxy acrylate
- refractive
- 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.)
- Granted
Links
Images
Landscapes
- Epoxy Resins (AREA)
- Optical Filters (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The high-refractive-index blue-light-proof modified epoxy acrylate material comprises the following components: 60-80 parts of modified epoxy acrylate monomer; 0-10 parts of urethane acrylate monomer; 3-15 parts of core-shell zinc selenide nano microsphere solution; 1-5 parts of photoinitiator; 0.1 to 0.5 weight portion of defoaming agent; 0.05 to 0.1 portion of light absorbent. The material is prepared into a blue-light-proof coating through photo-curing, and the refractive index (ne) of the coating is as follows: ultraviolet spectrum transmittance (t) of 1.66-1.70 and 280-380nm v )≤0.1％，385-415nm short wave blue light spectral transmittance (t) v ) Less than or equal to 0.1 percent and the transmittance (t) of short-wave blue light in the range of 415-445nm v ) Transmittance of < 35%,445-500nm of medium and long wavelength blue light (t) v ) Not less than 75%, visible light transmittance (t) in the range of 500-780nm v ) Not less than 89%, and has the advantages of short curing time, high visible light transmittance, good blue light protection effect, energy conservation and environmental protection.
Description
Technical Field
The invention belongs to the technical field of optometry new materials, particularly relates to the field of photocuring resin materials, and particularly relates to a photocuring high-refractive-index blue-light-proof modified epoxy acrylate coating material with an inorganic/organic composite structure and an optical filter.
Background
The resin material with high refractive index is widely applied to the manufacturing fields of optical lenses, optical fiber communication materials, ophthalmic applications, LED packaging, advanced optical device functional coatings and the like by virtue of the characteristics of impact resistance, processability, easy dyeing and light weight compared with inorganic glass. The continuous development of the optical devices is closely related to the development of high-refractive-index materials, the higher the refractive index is, the thinner the material achieving the same display effect is, and the functional material with the higher refractive index is more suitable for manufacturing advanced optical devices.
The ultraviolet curing is to decompose a photoinitiator by using ultraviolet light to generate active groups, and to initiate polymerization reaction by using the active groups to cure and crosslink the material. Compared with thermal curing and natural curing, the ultraviolet curing technology has the advantages of high forming speed, high energy utilization rate, environmental friendliness and excellent performance of finished products, and can be used for continuous daily production. China is the largest world lens producing country, and the quantity accounts for about 80 percent of the world; energy conservation, environmental protection and safety are great trends of industry development, so that the light-cured resin monomer with high refractive index has great application prospects in the field of optical components.
Selenium and sulfur are in the same period of the periodic table, and the molar refractive index of selenium atoms (R = 11.17) is much higher than that of sulfur atoms (R = 7.69); meanwhile, the zinc selenide nanometer material is a transparent polycrystalline material, and has good ultraviolet and blue light absorption effect, high light transmittance, large refractive index and strong thermal shock. However, the doping of inorganic selenide nanomaterials with organic polymers has two disadvantages: first, selenides tend to aggregate because of their high specific surface area, are difficult to disperse uniformly into the polymer matrix, and the optical transmission of the resulting material is severely limited due to light scattering by large size nanoparticles (> 20 nm). Secondly, due to the rigid nature of the inorganic components, the mechanical properties of these materials are unstable and film-forming properties of the films are difficult. Therefore, it is difficult to introduce zinc selenide into the optical resin matrix to increase the refractive index, and it is necessary to select a suitable method to improve the above problems.
Disclosure of Invention
The invention aims to provide a high-refractive-index blue-light-proof modified epoxy acrylate material and an optical filter. The material is photo-cured to prepare the blue light prevention coating, is quickly cured and molded under the irradiation of ultraviolet light, and has the advantages of short curing time, high visible light transmittance, good blue light protection effect, high bonding firmness of the coating and a matrix, energy conservation and environmental protection.
In order to realize the purpose, the invention comprises the following technical scheme:
a high-refractive-index blue-light-proof modified epoxy acrylate material comprises the following components:
(1) 60-80 parts by weight of a modified epoxy acrylate monomer represented by formula I;
(2) 0 to 10 parts by weight of a urethane acrylate monomer;
(3) 3-15 parts by weight of core-shell zinc selenide nano microsphere solution;
(4) 1-5 parts by weight of a photoinitiator;
(5) 0.1 to 0.5 part by weight of a defoaming agent;
(6) 0.05 to 0.1 part by weight of a light absorber;
the core of the core-shell type zinc selenide nano microsphere is zinc selenide, and the shell is a surfactant;
the solvent of the core-shell zinc selenide nano microsphere solution is an active diluent, and the weight ratio of the nano microspheres to the solvent is 1: (3-9);
the active diluent is an oxygen-containing acrylate compound;
the light absorbent is one or more of octaethyl porphin zinc, octaethyl porphin nickel and tetraphenyl porphin zinc.
The high-refractive-index blue-light-proof modified epoxy acrylate material is characterized in that the polyurethane acrylate monomer is a prepolymer obtained by reacting isocyanate and a hydroxyl acrylate derivative or a reaction product of dipentaerythritol acrylate modified by alkylene oxide and polyisocyanate.
In the high refractive index blue light prevention modified epoxy acrylate material, preferably, the urethane acrylate monomer is aromatic polyether urethane, aliphatic urethane diacrylate, aromatic polyether urethane triacrylate, aliphatic urethane triacrylate and/or aromatic urethane hexaacrylate.
Preferably, the urethane acrylate monomer of the present invention may use trade names: and urethane acrylate monomers such as SM6201, SM6205, SM6240, SM6318, SM6324, and SM 6501.
The high-refractive-index blue-light-proof modified epoxy acrylate material is preferably prepared by using a non-ionic surfactant or an anionic surfactant.
Preferably, the surfactant is polyoxyethylene ether, alkylbenzene sulfonate, alkyl sulfonate, petroleum sulfonate, polyoxyethylene ether and/or mercapto carboxylic acid.
Preferably, the reactive diluent is one or a mixture of more of o-phenylphenoxyethyl acrylate, ethoxyphenol acrylate, biphenyl methanol acrylate, 1, 6-hexanediol diacrylate, benzyl acrylate, pentaerythritol triacrylate, or trimethylolpropane triacrylate.
Preferably, the particle size of the core-shell zinc selenide nano-microspheres is 3-10 nm, and the mass ratio of zinc selenide to the surfactant is 1: 0.1-0.3.
Preferably, the core-shell zinc selenide nanoparticle solution is prepared by the following method:
adding sodium borohydride into deionized water, adding selenium powder after dissolving under the protection of nitrogen, reacting under stirring until Se powder disappears, and changing into a colorless transparent solution, wherein the mass ratio of the sodium borohydride to the Se powder to the water is (2-5) to (0.5-1) to (6-15); sequentially adding a surfactant and zinc chloride under stirring, wherein the mass ratio of the zinc chloride to the Se powder to the surfactant is (1-2) to (0.5-1) to (1-3); adjusting the pH value to 10-11 with sodium hydroxide solution, heating the solution to 65-100 ℃, refluxing for 3-5 hours, adding acetone to enable ZnSe to generate flocculent precipitate, separating, washing and drying to obtain core-shell type zinc selenide nano microspheres; and adding the core-shell type zinc selenide nano microspheres into an active diluent, and uniformly stirring to obtain a core-shell type zinc selenide nano microsphere solution.
Preferably, the photoinitiator is one or more of TPO, 184, 1173, 127 or methyl benzoylformate.
Preferably, the defoamer is one or more of a T-1000A type defoamer, a DS100 silicone oil defoamer, an AT350 polyether type defoamer or a D90 acrylic acid polymerization type defoamer.
On the other hand, the invention provides a high-refractive-index blue-light-proof filter, which is formed by coating the high-refractive-index blue-light-proof modified epoxy acrylate material on an optical material substrate to form a blue-light-proof coating.
In the high refractive index blue light blocking filter as described above, preferably, the optical material substrate is a thermosetting optical resin substrate, a thermoplastic optical plastic substrate, or optical glass.
In a preferred embodiment of the present invention, the modified epoxy acrylate monomer represented by formula I is prepared as follows:
i. synthesis of a Sulfur-containing epoxy resin monomer of formula II
Dissolving dimercapto diphenyl sulfide in 10-30 wt% sodium hydroxide solution, filtering, dripping the filtrate into a container of epoxy chloropropane, placing the container in a water bath at 50-70 ℃ under the protection of nitrogen, stirring in the midway, standing for reaction for 30-45min, stirring, adding methyl isobutyl ketone for extraction and liquid separation, washing an organic phase with hot water at 50-60 ℃ to remove chloride ions, separating an organic layer, and drying in vacuum at 60-80 ℃ to obtain a sulfur-containing epoxy resin monomer shown in a formula II; wherein, the mass ratio of the dimercapto diphenyl sulfide, the sodium hydroxide solution and the epoxy chloropropane is (0.7-1) to (1-3) to (9-12);
ii, synthesizing the modified epoxy acrylate monomer shown as the formula I
Adding a sulfur-containing epoxy resin monomer of formula II, a triethyl benzyl ammonium chloride catalyst and a polymerization inhibitor into a reaction container, wherein the mass ratio of the sulfur-containing epoxy resin monomer of formula II to the triethyl benzyl ammonium chloride catalyst to the polymerization inhibitor is 100: 1-2: 0.5-1; after the temperature is raised to 75 ℃, dripping acrylic acid, heating the sulfur-containing epoxy resin monomer and the acrylic acid to 80-90 ℃ to react for 4-8 hours in a dark condition, wherein the mass ratio of the sulfur-containing epoxy resin monomer to the acrylic acid is (0.8-1) to 1; adding dichloromethane and decolorizing adsorbent attapulgite, stirring, standing for layering, filtering to remove the adsorbent, and removing dichloromethane solvent by reduced pressure distillation to obtain colorless transparent modified epoxy acrylate monomer.
The high-refractive-index blue-light-proof modified epoxy acrylate material comprises the following main components:
1. a modified epoxy acrylate monomer (OEA) of formula I
The monomer is obtained by the esterification reaction of carboxyl of acrylic acid and epoxy group in dimercapto diphenyl sulfide epoxy resin, and the structural formula is as follows:
the monomer contains a plurality of sulfur elements and has higher refractive index. After the dimercapto diphenyl sulfide epoxy resin is modified by acrylic acid, on one hand, ultraviolet photosensitive active groups C = C are introduced, so that the monomer can carry out photocuring reaction; on the other hand, the monomer branched chain is a flexible long-chain structure, and the cured resin has good toughness and firmness and improves the mechanical property of the coating.
2. Urethane acrylate monomer (PUA)
Urethane acrylate monomer (PUA) can be added into the modified epoxy acrylate material, so that the bonding firmness of the coating and the resin base material is further enhanced.
3. The core-shell zinc selenide nanospheres have the following functions:
(1) The zinc selenide can improve the refractive index of the resin coating;
(2) The zinc selenide can absorb ultraviolet light and blue light of partial wave bands;
(3) The zinc selenide nano-microspheres can be used as a photocuring catalyst, the three-dimensional space is in a nanoscale range, the energy level change caused by the quantum size effect catalyzes the activity of a photoinitiator, the viscosity of a photocuring system is increased, the gel effect is more obvious, the double bond conversion rate of a coating is improved, photocuring is not affected by ultraviolet absorption, and the curing speed is high.
(4) The core-shell ZnSe nano material is prepared by modifying a ZnSe surfactant, so that the compatibility and the dispersibility of the inorganic material in an acrylate system are enhanced. In a preferred embodiment, the core-shell ZnSe microspheres are firstly dissolved in a reactive diluent and then added into the modified epoxy acrylate material, wherein the reactive diluent is an oxygen-containing acrylate compound, and the reactive diluent mainly participates in a photocuring reaction to form a resin material while the viscosity of the system is reduced.
4. Light absorbing agent
The conventional blue-light-proof material comprises an ultraviolet absorbent, but for ultraviolet light-initiated photocuring reaction, the addition of the ultraviolet absorbent can absorb certain ultraviolet light to influence the photocuring speed. According to the invention, a group of porphine metal complexes is unexpectedly found when a blue light absorbing material is selected, wherein the porphine metal complexes absorb part of ultraviolet light, but have higher transmittance in a 300nm ultraviolet spectrum region and have partial absorption of blue light. When the blue-light-resistant coating is matched with ZnSe for use, the absorption spectral lines of the two materials are in red shift, and the blue-light-resistant coating can absorb all ultraviolet light and over 65% of harmful blue light of medium and short waves, so that the coating has excellent blue light resistance.
The invention has the beneficial effects that: the high-refractive-index blue-light-proof modified epoxy acrylate material is quickly cured and molded under the irradiation of ultraviolet light, and the curing time is about 30 seconds. The coating has a high refractive index (n) e ): 1.66-1.70, ultraviolet spectrum transmittance (tv) of 280-380nm is less than or equal to 0.1%, short-wave blue light spectrum transmittance (t) of 385-415nm v ) Less than or equal to 0.1 percent and the transmittance (t) of short-wave blue light in the range of 415-445nm v ) Transmittance of < 35%,445-500nm of medium and long wavelength blue light (t) v ) 75 percent or more, visible light transmittance (tv) in the range of 500-780nm or more 89 percent, has the advantages of short curing time, high visible light transmittance, good blue light protection effect, energy conservation, environmental protection and firm combination of the film layer and the base material, and has extremely high application prospect and commercial value.
Drawings
Fig. 1 is a transmission electron microscope photograph of core-shell zinc selenide (PA 01) nanospheres prepared in accordance with an embodiment.
Fig. 2 is an infrared spectrum of a core-shell zinc selenide (PA 01) nanocrystal prepared by the embodiment.
FIG. 3 is an infrared spectrum of a modified epoxy acrylate monomer prepared in example 1.
FIG. 4 is a H-NMR spectrum of a modified epoxy acrylate monomer prepared in example 1.
FIG. 5 is a graph of the transmittance spectra of the high refractive blue-blocking coating prepared in example 1 and the coatings prepared in comparative examples 1 and 2.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
The zinc selenide nano microsphere transparent solution in the following embodiments is prepared by the following method:
reacting sodium borohydride with Se powder in water to generate sodium hydroselenide, sodium tetraborate and hydrogen, and reacting the sodium hydroselenide with zinc chloride under an alkaline condition to generate zinc selenide and zinc selenide salt; sodium tetraborate reacts with alkali to form borate, which has the following reaction formula:
NaBH 4 +Se+H 2 O→NaHSe+Na 2 B 4 O 7 +H 2 ↑
NaHSe+ZnCl 2 +NaHO→ZnSe+NaCl
Na 2 B 4 O 7 +NaHO→NaBO 2 +H 2 O
the specific operation for preparing the core-shell zinc selenide nanoparticle transparent solution is as follows:
a. adding 450g of sodium borohydride into 1000g of deionized water, protecting with nitrogen, dissolving, adding 60g of selenium powder, reacting by magnetic stirring to obtain a colorless transparent solution, sequentially adding 15g of sorbitol ester, 145g of thioglycolic acid and 160g of zinc chloride by stirring, adjusting the pH value to 11 by using 30% sodium hydroxide alkali solution, heating the solution to 90 ℃, refluxing for 3 hours, adding acetone to enable ZnSe to generate flocculent precipitates, separating, washing and drying to obtain the core-shell zinc selenide nanocrystal (PA 01).
b. Adding 100g of PA01 into a mixed diluent of 150g of ethoxyphenol acrylate and 500g of o-phenylphenoxyethyl acrylate, and uniformly stirring to obtain a ZnSe transparent solution (PA 02).
Observing the PA01 prepared in the step (a) by using a JEM-2100 type transmission electron microscope, wherein the appearance is in a cubic sphere shape as shown in figure 1, the color of a ZnSe nanocrystal core is light yellow, a shell is thioglycolic acid and is coated around the nanocrystal in a carboxylate form, and the outer shell of the carboxylate is a colorless transparent material, so that a white aperture is displayed in a transmission electron microscope picture and is a ZnSe/thioglycolic acid core-shell structure; the diameter of the core-shell ZnSe nanosphere is about 4.2nm as calculated by the Sherrer equation (D = K/beta cos theta) and Zeta potential analysis.
The PA01 prepared in step (a) was subjected to Fourier transform infrared spectroscopy (FT-IR), and 700cm by curve analysis in FIG. 2 -1 The absorption peak at (B) is a stretching vibration peak of C-S in the surface modifier, and is influenced by a Zn-S coordinate bond to generate a little displacement of 1384cm -1 And 1570nm -1 The absorption peak appeared here is a characteristic absorption peak of the carboxylate of the surface outer shell, further illustrating that O-H in the surfactant is cleaved and forms carboxylate with cations in the solution at 2980cm in the preparation of ZnSe particles by synthesis -1 The absorption peak appearing at is-CH 2- The stretching vibration peak of (1).
Example 1: preparation of modified epoxy acrylate monomer, high-refraction blue-light-proof coating material and optical filter
Preparing a modified epoxy acrylate monomer:
I. dissolving 90g of dimercaptodiphenyl sulfide in 180g of 25% sodium hydroxide solution, filtering, dropwise adding the filtrate into a container containing 950g of epoxy chloropropane, placing the mixture in a water bath at 60 ℃ under the protection of nitrogen, stirring in the midway after completing dripping within 60min, standing for reaction for 30min, extracting and separating liquid by using methyl isobutyl ketone, washing an organic phase by hot water at 55 ℃ to remove chloride ions, separating an organic layer, and drying in vacuum at 65 ℃ to obtain the sulfur-containing epoxy resin monomer shown in the formula II.
II, adding 31g of the prepared sulfur-containing epoxy resin monomer, 0.45g of triethylbenzylammonium chloride and 0.21g of 4-methoxyphenol into a three-neck flask, heating to 75 ℃, dropwise adding 33g of acrylic acid, heating to 85 ℃ in the dark to react for 5 hours, adding 70g of dichloromethane and 25g of attapulgite powder to perform purification and decoloration treatment, stirring for 35 minutes, standing for layering, filtering to remove an adsorbent, and performing reduced pressure evaporation to remove a dichloromethane solvent to obtain a colorless and transparent modified epoxy acrylate monomer (formula I), wherein the yield is 87.9%.
Fourier transform Infrared Spectroscopy (FTIR) measurements were performed on the modified epoxy acrylate monomer prepared in step II, see FIG. 3, at 1720cm -1 The C = O peak appears at 1630cm -1 The C = C peak appears at 3400cm -1 The area of the-OH peak at (A) is increased, which proves that acrylic acid has undergone esterification with epoxy resin.
An H-NMR spectrum analysis of the modified epoxy acrylate monomer prepared in step II is performed, see fig. 4,7.26ppm is a solvent peak of chloroform, 8H of benzene ring appear at 7.23 to 7.35ppm, 6H on terminal C = C appears at 6.40 to 5.80ppm, 8H of two methylene groups appear at 4.41 to 4.24ppm, 2H of methylene group connecting hydroxyl group appears at 4.49ppm, 2H of hydroxyl group appears at 5.37ppm, and 4H of methylene group connecting S ether appears at 3.12 to 3.16 ppm.
(II) preparing a high-refraction blue-light-proof coating material:
weighing 38g of modified epoxy acrylate monomer prepared in the step II, sequentially adding 4g of PA02, 3g of PUA (SM 6205), 0.1g of defoaming agent T-1000A and 0.026g of octaethylporphyrin nickel, stirring for 35min, adding 1.1g of 1173 photoinitiator, stirring for 10min in the dark, and storing in the dark.
(III) preparing high-refraction blue-light-proof coating optical filter
And (3) heating the coating material prepared in the step (II) to 40 ℃, quickly spin-coating the coating on the surface of the PMMA optical substrate at 2500 rpm, then placing the coated substrate under a UV-LED light curing machine with the light irradiation height of 20cm for irradiating for 28s, and completely curing the coating to obtain the high-refraction blue-light-proof coating optical filter.
Example 2: preparation of modified epoxy acrylate monomer, high-refraction blue-light-proof coating material and optical filter
Preparing a modified epoxy acrylate monomer:
I. dissolving 85g of dimercapto diphenyl sulfide in 185g of 25% sodium hydroxide solution, filtering, dropwise adding the filtrate into a container of 900g of epichlorohydrin, placing the mixture in a water bath at 60 ℃ under the protection of nitrogen, stirring the mixture midway after completing dropwise addition within 60min, standing the mixture for reaction for 30min, extracting and separating the mixture by using methyl isobutyl ketone, washing an organic phase by hot water at 60 ℃ to remove chloride ions, separating an organic layer, and drying the organic layer in vacuum at 65 ℃ to obtain the sulfur-containing epoxy resin monomer shown in the formula II.
And II, adding 30g of the prepared sulfur-containing epoxy resin monomer, 0.42g of triethylbenzylammonium chloride and 0.25g of 4-methoxyphenol into a three-neck flask, heating to 75 ℃, dropwise adding 33g of acrylic acid, heating to 85 ℃ in the dark to react for 5 hours, adding 70g of dichloromethane and 25g of attapulgite powder to perform purification and decoloration treatment, stirring for 35 minutes, standing for layering, filtering to remove an adsorbent, and performing reduced pressure evaporation to remove a dichloromethane solvent to obtain a colorless and transparent modified epoxy acrylate monomer, wherein the yield is 87.6%.
Fourier transform infrared spectroscopy (FTIR) testing and H-NMR spectrum analysis are carried out on the modified epoxy acrylate monomer obtained in the step II, and the detection result is basically the same as that of the example 1.
(II) preparing a high-refraction blue-light-proof coating material:
weighing 38g of modified epoxy acrylate monomer prepared in the step (one), sequentially adding 2g of PA02, 0.1g of defoaming agent T-1000A and 0.026g of octaethyl porphin zinc, stirring for 35min, adding 1.1g of 1173 photoinitiator, stirring for 10min in the dark, and storing in the dark.
(III) preparing high-refraction blue-light-proof coating optical filter
And (3) heating the coating material prepared in the step (II) to 40 ℃, quickly spin-coating the coating material on the surface of the PMMA optical substrate at 2500 rpm, then placing the coating substrate under a UV-LED light curing machine with the light irradiation height of 20cm for irradiating for 30s, and completely curing the coating to obtain the high-refraction blue-light-proof coating optical filter.
Example 3: preparation of high-refraction blue-light-proof coating material and optical filter
Preparing a high-refraction blue-light-proof coating material:
weighing 38g of the modified epoxy acrylate monomer prepared in example 1, sequentially adding 6g of PA02, 2g of PUA (SM 6201), 0.1g of defoamer T-1000A and 0.025g of octaethyl porphin nickel, stirring for 35min, adding 1.1g of 1173 photoinitiator, stirring for 10min in the dark, and storing in the dark.
(II) preparing high-refraction blue-light-proof coating optical filter
And (2) heating the coating material prepared in the step (I) to 40 ℃, quickly spin-coating the coating material on the surface of the optical glass substrate at 2500 rpm, then placing the coating substrate under a UV-LED (ultraviolet-light emitting diode) photocuring machine with the illumination height of 20cm for irradiating for 26s, and completely curing the coating to obtain the high-refraction blue-light-proof coating optical filter.
Example 4: preparation of high-refraction blue-light-proof coating material and optical filter
Preparing a high-refraction blue-light-proof coating material:
38g of the modified epoxy acrylate monomer prepared in example 1 was weighed, added with 3g of PA02, 3g of SM6205, 0.1g of defoamer T-1000A and 0.03g of octaethylporphyrin nickel in sequence, stirred for 35min, added with 1.1g of 1173 photoinitiator, stirred for 10min in the dark, and stored in the dark.
(II) preparing high-refraction blue-light-proof coating optical filter
And (2) heating the coating material prepared in the step (I) to 40 ℃, quickly spin-coating the coating material on the surface of the PC substrate at 2500 rpm, then placing the coating substrate under a UV-LED (ultraviolet-light emitting diode) photocuring machine with the illumination height of 20cm, and irradiating for 32s, so that the coating is completely cured, and the high-refraction blue-light-proof coating optical filter is obtained.
Example 5: preparation of high-refraction blue-light-proof coating material and optical filter
Preparing a high-refraction blue-light-proof coating material:
38g of the modified epoxy acrylate monomer prepared in example 1 was weighed, and 5g of PA02, 0.1g of defoamer T-1000A and 0.024g of octaethyl porphin nickel were added in this order, stirred for 35min, then 1.1g of 1173 photoinitiator was added, stirred for 10min in the dark, and stored in the dark.
(II) preparing high-refraction blue-light-proof coating optical filter
And (2) heating the coating material prepared in the step (I) to 40 ℃, quickly spin-coating the coating material on the surface of the optical glass substrate at 2500 rpm, then placing the coating substrate under a UV-LED (ultraviolet-light emitting diode) photocuring machine with the illumination height of 20cm for irradiating for 26s, and completely curing the coating to obtain the high-refraction blue-light-proof coating optical filter.
Example 6: preparation of high-refraction blue-light-proof coating material and optical filter
Preparing a high-refraction blue-light-proof coating material:
weighing 38g of the modified epoxy acrylate monomer prepared in example 1, sequentially adding 3.5g of PA02, 0.1g of defoamer T-1000A and 0.026g of tetraphenylporphyrin zinc, stirring for 35min, adding 1.1g1173 of photoinitiator, stirring for 10min in the dark, and storing in the dark.
(II) preparing high-refraction blue-light-proof coating optical filter
And (2) heating the coating material prepared in the step (I) to 40 ℃, quickly spin-coating the coating material on the surface of the PC substrate at 2500 rpm, then placing the coating substrate under a UV-LED (ultraviolet-light emitting diode) photocuring machine with the illumination height of 20cm, and irradiating for 30s, so that the coating is completely cured, and thus the high-refraction blue-light-proof coating optical filter is obtained.
Comparative example 1: preparation of modified epoxy acrylate coating material containing light absorber and optical filter
Preparing a coating material:
weighing 38g of modified epoxy acrylate monomer prepared in example 1, sequentially adding 3g of SM6205, 0.1g of defoamer T-1000A and 0.026g of octaethylporphyrin nickel, stirring for 35min, adding 1.1g of 1173 photoinitiator, stirring for 10min in the dark, and storing in the dark.
(II) preparing a coated optical filter
And (2) heating the coating material prepared in the step (I) to 40 ℃, quickly spin-coating the coating material on the surface of the PMMA optical substrate at 2500 rpm, then placing the coating substrate under a UV-LED light curing machine with the light irradiation height of 20cm for irradiating for 60s, and completely curing the coating to obtain the modified epoxy acrylate coating optical filter containing the light absorber.
Comparative example 2: preparation of zinc selenide-containing modified epoxy acrylate coating material and optical filter
Preparing a coating material:
weighing 38g of modified epoxy acrylate monomer prepared in example 1, sequentially adding 4g of PA02, 3g of SM6205 and 0.1g of defoamer T-1000A, stirring for 35min, adding 1.1g of 1173 photoinitiator, stirring for 10min in the dark, and storing in the dark.
(II) preparing a coated optical filter
Heating the coating material prepared in the step (I) to 40 ℃, quickly spin-coating the coating material on the surface of the PMMA optical substrate at 2500 rpm, then placing the coating substrate under a UV-LED (ultraviolet-light emitting diode) light curing machine with the illumination height of 20cm, irradiating for 23s, and completely curing the coating to obtain the modified epoxy acrylate coating optical filter containing zinc selenide.
Experimental example 1: light transmission performance detection experiment
The coatings prepared in examples 1 to 6 and comparative examples 1 to 2 were respectively subjected to transmittance test, transmittance (transmittance) test, and test results are shown in table one, using a UV-8000 UV-vis spectrophotometer manufactured by shanghai chromatography instruments ltd.
TABLE-measurement of spectral transmittance (tv) of a sample
And (4) conclusion: the results in Table I show that the UV spectral transmittance (tv) of 280-380nm and short-wave blue spectral transmittance (t) of 385-415nm of the coated filters of examples 1-6 are less than or equal to 0.1 percent v ) Less than or equal to 0.1 percent and the transmittance (t) of short-wave blue light in the range of 415-445nm v ) Transmittance of < 35%,445-500nm of medium and long wavelength blue light (t) v ) 75% or more, visible light transmittance (tv) in the range of 500-780nm or more 89%, high visible light transmittance and good blue light protection effect.
Fig. 5 is a graph comparing transmittance spectra of the high-refractive blue-light-blocking coating prepared in example 1 and the coatings prepared in comparative examples 1 and 2. As can be seen, the effective absorption spectral line of example 1 is red-shifted from 415nm to 445nm, compared to comparative example 1 containing only a light absorber; the absorption spectrum line is also red-shifted relative to comparative example 2, which contains only zinc selenide. The zinc selenide nano-microspheres and the light absorber act synergistically in the coating without the ultraviolet absorber, and efficiently absorb 385-445nm short-wave harmful blue light and ultraviolet rays, and the transmittance of the short-wave blue light is low.
Experimental example 2: high refractive anti-blue light photosensitive coating refractive index detection
The high-refraction blue-light-proof photosensitive coating materials prepared in examples 1 to 6 were subjected to refractive index detection respectively by using a WZS1 Abbe refractometer manufactured by Shanghai optical instruments and Equipment Co., ltd, and the detection method was: the sample is directly coated on a prism of an Abbe refractometer to measure the refractive index, and the detection result is shown in the second table.
TABLE II refractive index (nd) of sample
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| nd | 1.695 | 1.659 | 1.724 | 1.675 | 1.706 | 1.687 |
Experimental example 3: photocuring detection test
Weighing 38g of the modified epoxy acrylate monomer prepared in example 1, adding 5g of PA02, 0.1g of defoamer T-1000A and 0.024g of UV-327, stirring for 35min, adding 1.1g of 1173 photoinitiator, stirring for 10min in the dark, heating to 40 ℃, quickly spin-coating the coating on the surface of the resin sheet substrate at 2500 rpm, and then placing the coating sheet under a UV-LED photocuring machine with the illumination height of 20cm for irradiation. The preparation and detection were carried out by replacing different UV absorbers in the same manner as described above, and the types and amounts of the UV absorbers are shown in Table three. The time required for complete curing of the coating was recorded and the results are shown in table three.
TABLE III determination of the time required for photocuring of the samples
| Sample (I) | 1# | 2# | 3# | 4# | 5# |
| Ultraviolet absorber | UV-327 | UV-327 | UV-P | UV-326 | UV-531 |
| Adding amount of | 0.024g | 0.125g | 0.095g | 0.114g | 0.069g |
| Curing time | 3 minutes and 40 |
10 minutes | 8 minutes and 30 seconds | 9 minutes and 10 |
6 minutes and 50 seconds |
The results in table three show that the light-induced efficiency of the light-cured system consisting of the ultraviolet absorbent and the modified epoxy acrylate monomer is reduced due to the obstruction and influence of the ultraviolet absorbent, so that the final conversion rate of double bonds is reduced, and the curing time is prolonged. The photocuring time of the coating of example 5, which parallels the experimental conditions described above, is only 26s. The light curing system composed of zinc selenide, the light absorbent and the modified epoxy acrylate monomer has small influence on photoinitiation efficiency, can form a cross-linked network in a short time, and has the advantages of increased double bond conversion rate and obvious gel effect.
Experimental example 4: film firmness detection experiment
Respectively carrying out a cross-cut lattice test by a tape method on the optical filter film layers prepared in the embodiments 1 to 6, and detecting according to GB 10810.4-2012 national standard: scratching the surface of the optical filter by using an art designing blade, scratching the surface of the optical filter from a vertical angle, finally leaving more than 25 square small squares on the surface of the optical filter, adhering a 3M invisible adhesive tape on the squares, and tearing the adhesive tape backwards at a slightly quick and stable speed. The cross-cut experimental result shows that the film layer does not fall off and the firmness of the film layer is qualified.
Experimental example 5: film flexibility test
The coating monomers prepared in examples 1 to 6 were respectively subjected to a flexibility test, according to GB1731 "paint film flexibility determination method", using a flexibility tester, and the specific operation steps were as follows: and (3) upward pressing the cured test plate film layer on a shaft rod with a specified diameter by using two hands, bending the test plate around the shaft rod within 2-3 s by using the force of two thumbs, and observing the film layer by using a magnifying glass after bending.
Claims (10)
1. The high-refractive-index blue-light-proof modified epoxy acrylate material is characterized by comprising the following components:
(1) 60-80 parts by weight of a modified epoxy acrylate monomer represented by formula I;
(2) 0 to 10 parts by weight of a urethane acrylate monomer;
(3) 3-15 parts by weight of core-shell zinc selenide nanosphere solution;
(4) 1-5 parts by weight of a photoinitiator;
(5) 0.1 to 0.5 part by weight of a defoaming agent;
(6) 0.05 to 0.1 part by weight of a light absorber;
the core of the core-shell type zinc selenide nano microsphere is zinc selenide, and the shell is a surfactant;
the solvent of the core-shell zinc selenide nano microsphere solution is an active diluent, and the weight ratio of the nano microspheres to the solvent is 1: 3-9;
the active diluent is an oxygen-containing acrylate compound;
the light absorbent is one or more of octaethyl porphin zinc, octaethyl porphin nickel and tetraphenyl porphin zinc.
2. The high refractive index blue light-blocking modified epoxy acrylate material of claim 1 wherein the urethane acrylate monomer is a prepolymer of the reaction of an isocyanate with an acrylate derivative of a hydroxyl group or the reaction product of an alkylene oxide modified dipentaerythritol acrylate with a polyisocyanate.
3. The high refractive index blue light-proof modified epoxy acrylate material according to claim 3, wherein the urethane acrylate monomer is aromatic polyether urethane, aliphatic urethane diacrylate, aromatic polyether urethane triacrylate, aliphatic urethane triacrylate and/or aromatic urethane hexaacrylate.
4. The high refractive index blue-light preventing modified epoxy acrylate material according to claim 1, wherein the surfactant is a nonionic surfactant or an anionic surfactant, preferably the surfactant is polyoxyethylene ether, alkylbenzene sulfonate, alkyl sulfonate, petroleum sulfonate, polyoxyethylene ether and/or mercapto carboxylic acid.
5. The high-refractive-index blue-light-proof modified epoxy acrylate material as claimed in claim 1, wherein the reactive diluent is one or a mixture of more of o-phenylphenoxyethyl acrylate, ethoxyphenol acrylate, biphenyl methyl alcohol acrylate, 1, 6-hexanediol diacrylate, benzyl acrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate.
6. The high-refractive-index blue-light-proof modified epoxy acrylate material as claimed in claim 1, wherein the particle size of the core-shell zinc selenide nano-microspheres is 3-10 nm, and the mass ratio of zinc selenide to surfactant is 1: 0.1-0.3.
7. The high-refractive-index blue-light-proof modified epoxy acrylate material as claimed in any one of claims 1 to 6, wherein the core-shell zinc selenide nano microsphere solution is prepared by a method comprising:
adding sodium borohydride into deionized water, adding selenium powder after dissolving under the protection of nitrogen, reacting under stirring until Se powder disappears, and obtaining a colorless transparent solution, wherein the mass ratio of the sodium borohydride to the Se powder to the water is (2-5) to (0.5-1) to (6-15); sequentially adding a surfactant and zinc chloride under stirring, wherein the mass ratio of the zinc chloride to the Se powder to the surfactant is (1-2) to (0.5-1) to (1-3); adjusting the pH value to 10-11 with sodium hydroxide solution, heating the solution to 65-100 ℃, refluxing for 3-5 hours, adding acetone to enable ZnSe to generate flocculent precipitate, separating, washing and drying to obtain core-shell type zinc selenide nano microspheres; adding the core-shell type zinc selenide nanospheres into an active diluent, and stirring uniformly to obtain a core-shell type zinc selenide nanosphere solution.
8. The high-refractive-index blue-light-proof modified epoxy acrylate material as claimed in any one of claims 1 to 6, wherein the photoinitiator is one or more of TPO, 184, 1173, 127 or methyl benzoylformate.
9. The high-refractive-index blue-light-proof modified epoxy acrylate material as claimed in any one of claims 1 to 6, wherein the defoaming agent is one or more of T-1000A type defoaming agent, DS100 silicone oil type defoaming agent, AT350 polyether type defoaming agent or D90 acrylic acid polymerization type defoaming agent.
10. A high-refractive-index blue-light-proof optical filter is characterized in that the high-refractive-index blue-light-proof modified epoxy acrylate material as claimed in any one of claims 1 to 9 is coated on an optical material substrate to serve as a blue-light-proof coating; preferably, the optical material substrate is a thermosetting optical resin substrate, a thermoplastic optical plastic substrate, or an optical glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211609725.1A CN115785712B (en) | 2022-12-14 | 2022-12-14 | High-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211609725.1A CN115785712B (en) | 2022-12-14 | 2022-12-14 | High-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115785712A true CN115785712A (en) | 2023-03-14 |
| CN115785712B CN115785712B (en) | 2023-07-28 |
Family
ID=85420175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211609725.1A Active CN115785712B (en) | 2022-12-14 | 2022-12-14 | High-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115785712B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116716035A (en) * | 2023-06-09 | 2023-09-08 | 江苏视科新材料股份有限公司 | Filtering coating material capable of accurately regulating and controlling protection |
| CN116731498A (en) * | 2023-06-09 | 2023-09-12 | 江苏视科新材料股份有限公司 | Blue light-proof photochromic resin lens |
| CN117402550A (en) * | 2023-06-09 | 2024-01-16 | 江苏视科新材料股份有限公司 | Nano composite color filter coating liquid and filter |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993410A (en) * | 2012-11-30 | 2013-03-27 | 深圳职业技术学院 | Method for preparing sulfur-containing high-refractive-index resin |
| CN104877685A (en) * | 2015-06-17 | 2015-09-02 | 燕山大学 | Preparation method of ZnSe/ ZnS quantum dot for core-shell structure of photoelectric device |
-
2022
- 2022-12-14 CN CN202211609725.1A patent/CN115785712B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993410A (en) * | 2012-11-30 | 2013-03-27 | 深圳职业技术学院 | Method for preparing sulfur-containing high-refractive-index resin |
| CN104877685A (en) * | 2015-06-17 | 2015-09-02 | 燕山大学 | Preparation method of ZnSe/ ZnS quantum dot for core-shell structure of photoelectric device |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116716035A (en) * | 2023-06-09 | 2023-09-08 | 江苏视科新材料股份有限公司 | Filtering coating material capable of accurately regulating and controlling protection |
| CN116731498A (en) * | 2023-06-09 | 2023-09-12 | 江苏视科新材料股份有限公司 | Blue light-proof photochromic resin lens |
| CN116716035B (en) * | 2023-06-09 | 2023-12-15 | 江苏视科新材料股份有限公司 | Filtering coating material capable of accurately regulating and controlling protection |
| CN117402550A (en) * | 2023-06-09 | 2024-01-16 | 江苏视科新材料股份有限公司 | Nano composite color filter coating liquid and filter |
| CN117402550B (en) * | 2023-06-09 | 2024-05-10 | 江苏视科新材料股份有限公司 | Nano composite color filter coating liquid and filter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115785712B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115785712B (en) | High-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter | |
| CN116023813B (en) | Preparation method of high-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter | |
| KR100638123B1 (en) | Resin composition containing ultrafine inorganic particle | |
| CN101965373B (en) | Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition | |
| US8133428B2 (en) | Photocurable composition, process for producing fine patterned product and optical element | |
| KR101265411B1 (en) | Hardening composition and resultant hardened material | |
| KR101216817B1 (en) | Curable composition and cured product thereof | |
| TWI522413B (en) | Hardened resin composition | |
| Lin et al. | Preparation and characterization of novel ZnS/sulfur-containing polymer nanocomposite optical materials with high refractive index and high nanophase contents | |
| KR100787770B1 (en) | Coating composition for low refractive layer, anti-reflection film using the same and image displaying device comprising said anti-reflection film | |
| JP6131062B2 (en) | Curable resin composition, cured product thereof and optical material | |
| CN114163972A (en) | High-wettability environment-friendly three-proofing adhesive and preparation method thereof | |
| CN101775144A (en) | Fluorine silicon resin, preparation method thereof and antifouling paint | |
| CN114574091A (en) | UV-moisture dual-curing three-proofing paint for optical module and preparation method and application thereof | |
| CN114163974A (en) | UV-LED and moisture dual-curing high-wettability environment-friendly three-proofing adhesive and preparation method thereof | |
| US5047576A (en) | Polymerizable vinyl compound having polythioether skeleton | |
| EP1287047B1 (en) | Photo-polymers and use thereof | |
| JP2004217836A (en) | Radiation curing composition, method for producing radiation curing composition, cured product and optical material | |
| WO2019167461A1 (en) | Polymer-containing photocurable composition for imprinting use | |
| JP2004204206A (en) | Photocurable composition and its manufacturing method, as well as cured product | |
| CN111944077A (en) | High-refractive-index photosensitive resin and preparation method thereof | |
| CN113817382B (en) | Anti-reflection coating for enhancing thermal stability of film and preparation method and application thereof | |
| JPS63235332A (en) | Optical element | |
| CN115785811B (en) | High-refractive-index blue light prevention material and blue light prevention filter | |
| CN115785756B (en) | Preparation method of blue light prevention coating material with adjustable refractive index |
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 |