CN113093313A - Optical lens, preparation method thereof and application thereof in branched optical fiber device - Google Patents
Optical lens, preparation method thereof and application thereof in branched optical fiber device Download PDFInfo
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- CN113093313A CN113093313A CN202110393593.2A CN202110393593A CN113093313A CN 113093313 A CN113093313 A CN 113093313A CN 202110393593 A CN202110393593 A CN 202110393593A CN 113093313 A CN113093313 A CN 113093313A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The invention belongs to the technical field of optical lenses, and particularly relates to an optical lens, a preparation method thereof and application thereof in a bifurcated optical fiber device. The optical lens uses polycarbonate resin as a plastic substrate, a composition containing polyurethane resin, an organic silicon compound, metal oxide particles, a cross-linking agent, an ultraviolet absorbent and hydroxycyclohexane phenone is a hard film layer, and a composition containing the organic silicon compound and silicon dioxide is an anti-reflection film layer.
Description
Technical Field
The invention belongs to the technical field of optical lenses, and particularly relates to an optical lens, a preparation method thereof and application thereof in a bifurcated optical fiber device.
Background
An optical lens is an optical element made of a transparent material and having a spherical surface, and plays an important role in cameras, optical instruments, mobile phones, and the like. The optical lens materials mainly comprise two types of glass lenses and plastic lenses, wherein the glass lenses have excellent light transmittance and heat resistance and high dimensional stability, so that the glass lenses occupy a main position in the field of traditional high-end optical lenses, but the glass lenses are expensive and have complex processing technology, and the application of the optical lenses is limited. With the research on some novel optical polymer materials with high light transmittance, low hygroscopicity and good impact resistance, plastic lenses are increasingly widely used.
The optical lens is an indispensable optical device, and the material selection and the molding process have great influence on the performance of the optical lens. The plastic material for an optical lens is required to satisfy the following points: 1) the light transmittance is as large as possible in the wavelength range required to pass through; 2) have a higher refractive index, less or no birefringence; 3) the mechanical processing performance is good, and the impact resistance is good; 4) good physical and chemical stability, difficult shrinkage and deformation, aging resistance and chemical corrosion resistance; 5) the heat sensitivity is poor, and the overall dimension is not easily influenced by humidity and temperature. At present, the plastic lens materials mainly used include polycarbonate, polystyrene, polymethyl methacrylate, allyl diglycol dicarbonate, etc., and these materials all have certain disadvantages. In the processing process of the plastic lens, due to the inherent characteristics of the high polymer material, such as large thermal expansion and cold contraction effect, molecular orientation, birefringence and the like exist, and the high-quality requirement of the optical lens is difficult to meet by adopting a common processing technology. Therefore, to meet the increasing demand for high-quality optical lenses, further research into materials and processing techniques of the optical lenses is required.
Disclosure of Invention
The invention aims to provide an optical lens with high light transmittance, high refractive index, good adhesion between a plastic substrate and a hard film layer, good scratch resistance and excellent heat resistance and a preparation method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme.
The application of the polyurethane resin in preparing the optical lens is characterized in that the polyurethane resin is prepared by reacting sorbitol, 4-aminosalicylhydrazide modified fulvic acid and aliphatic diisocyanate.
The aliphatic diisocyanate is any one of xylylene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
The 4-aminosalicylhydrazide modified fulvic acid is prepared by the following method:
dispersing fulvic acid into water, adjusting the pH value to 10-12 by using a sodium hydroxide solution, adding formaldehyde, heating to 80-90 ℃, adding 4-aminosalicylhydrazide, heating to 90-100 ℃, reacting for 2-4 hours, naturally cooling to room temperature, adjusting the pH value to 4-5 by using a hydrochloric acid solution, heating to 95-100 ℃, reacting for 4-6 hours, and drying after the reaction is finished.
The mass ratio of the fulvic acid, the 4-aminosalicylhydrazide and the formaldehyde is 1: 1-1.5: 0.5-0.8.
The invention utilizes 4-aminosalicylhydrazide to modify fulvic acid, wherein the fulvic acid molecule contains various functional groups such as carboxyl, hydroxyl, ketocarbonyl and the like, and can react with amino in 4-aminosalicylhydrazide, and the modified fulvic acid makes up the defects of poor water resistance and poor heat-resistant stability; the polyurethane resin prepared by taking the 4-aminosalicylhydrazide modified fulvic acid as the synergistic component has high transparency, is beneficial to improving the light transmittance and the refractive index of a final product optical lens and improving the heat resistance of the optical lens, and probably because the modified fulvic acid is subjected to crosslinking reaction with aliphatic diisocyanate, is beneficial to increasing the crosslinking density of polyurethane, so that the heat resistance is improved; and the scratch resistance of the optical lens can be improved, probably because the yellow humic acid is modified by the 4-aminosalicylhydrazide, rigid group benzene rings are introduced into molecules, polar groups are increased, the degree of hydrogen bonding is increased, the surface hardness of polyurethane is improved, and thus the scratch resistance of the optical lens is improved.
The preparation method of the polyurethane resin comprises the following steps:
mixing 4-aminosalicylhydrazide modified fulvic acid and sorbitol, charging nitrogen, dehydrating for 1-4 h at 100-110 ℃, naturally cooling to 70-80 ℃, adding aliphatic diisocyanate, stirring for reacting for 1-3 h, reducing the temperature to room temperature, adding triethylamine, neutralizing for reacting for 30-50 min, adding into deionized water, stirring for 1-3 h at a high speed, and finally performing rotary evaporation at 40-60 ℃ to obtain the polyurethane resin.
The mass ratio of the sorbitol to the 4-aminosalicylhydrazide modified fulvic acid to the aliphatic diisocyanate is 1: 0.05-0.1: 0.3-0.5.
The addition amount of triethylamine is 0.02-0.05 times of the mass of sorbitol.
According to the invention, the 4-aminosalicylhydrazide modified fulvic acid is used as polyol, aliphatic diisocyanate is used as a cross-linking agent to prepare polyurethane resin, and the obtained polyurethane has high transparency, good scratch resistance, strong adhesiveness and excellent heat resistance; the polyurethane resin is used for preparing the hard film layer of the optical lens, so that high transparency and refractive index can be obtained, the scratch resistance is good, the heat resistance is excellent, the adhesion between the hard film layer and a plastic substrate is good, the stability is high, and the service life is long.
An optical lens, wherein the polyurethane resin is contained in a hard film layer of the optical lens.
The optical lens specifically includes: a plastic substrate, a hard film layer formed on the plastic substrate, and an antireflection film layer formed on the hard film layer; wherein the content of the first and second substances,
a plastic substrate, a polycarbonate resin;
a hard film layer comprising: 60 to 80 parts by weight of the polyurethane resin, 10 to 20 parts by weight of an organic silicon compound, 4 to 6 parts by weight of a crosslinking agent, 1 to 3 parts by weight of an ultraviolet absorber, 5 to 20 parts by weight of metal oxide fine particles, and 0.1 to 2 parts by weight of hydroxycyclohexane phenone;
an antireflective film layer comprising: 80-95 parts by weight of an organic silicon compound and 5-20 parts by weight of silicon dioxide.
The organic silicon compound is any one or more of vinyltriethoxysilane, diphenylvinylethoxysilane, methyl triisopropoxysilane, methyltriacetoxysilane, tetraphenoxysilane and mercaptopropyltriethoxysilane.
The metal in the metal oxide particles is selected from any two or more of Si, Al, Zn, Ti, Zr and Ce, and the particle size of the particles is 20-100 nm.
The ultraviolet absorbent is selected from any one of benzoate and benzoate derivatives, benzotriazole and benzophenone ultraviolet absorbents.
The crosslinking agent is any one of benzoyl peroxide, dicumyl peroxide, diethylenetriamine and divinylbenzene.
The particle size of the silicon dioxide is 60-120 nm.
According to the invention, the optical lens takes polycarbonate resin as a plastic substrate, the mixture containing polyurethane resin, organic silicon compound, metal oxide particles, cross-linking agent, ultraviolet absorbent and hydroxycyclohexane phenone is used as a hard film layer, and the mixture containing organic silicon compound and silicon dioxide is used as an anti-reflection film layer.
In the invention, the right amount of hydroxycyclohexane phenyl ketone is added into the hard film layer, so that the light resistance of the optical lens can be improved, and the hard film layer is not easy to yellow in the curing process, thereby obtaining higher light transmittance and refractive index; the heat resistance of the optical lens can be increased probably because the addition of the hydroxycyclohexane phenyl ketone can provide more active groups, contribute to forming a multi-crosslinked network structure, and improve the crosslinking density, thereby improving the heat resistance.
The preparation method of the optical lens comprises the following steps:
1) pretreating the polycarbonate resin by using a malic acid/oxaloacetic acid mixed solution;
2) coating the hard film layer composition on a plastic substrate and forming a hard film layer through ultraviolet curing, wherein the curing conditions are as follows: the ultraviolet illumination power is 800-1000W, and the curing time is 10-30 min;
3) coating the anti-reflection film layer composition on the hard film layer and forming the anti-reflection film layer through ultraviolet curing and thermocuring; the ultraviolet curing conditions are as follows: the ultraviolet illumination power is 800-1000W, and the curing time is 5-20 min; the thermosetting temperature is 100-120 ℃, and the curing time is 1-3 h.
According to the technical scheme, firstly, a mixed solution of malic acid and oxaloacetic acid is utilized to pretreat polycarbonate resin, then a hard film layer is formed on a plastic substrate, and then an antireflection film layer is formed on the hard film layer, so that the optical lens with high light transmittance, high refractive index, good scratch resistance, excellent heat resistance and strong adhesion between the hard film layer and the plastic substrate is obtained.
The specific steps of the step 1) are that the polycarbonate resin is placed in a malic acid/oxaloacetic acid mixed solution, treated for 0.5-2 h at 50-70 ℃, washed with water and dried at 80-100 ℃. The mass fraction of oxaloacetic acid in the mixed solution is 8-15%, and the mass fraction of malic acid is 5-10%. In the invention, the surface treatment is carried out on the polycarbonate by utilizing the malic acid/oxaloacetic acid mixed solution to remove impurities on the surface of polyurethane, so that the surface activity of the polycarbonate is improved, a compact hard film layer is formed on the surface of the polycarbonate, the adhesive force between the polycarbonate and the hard film layer can be increased, and the scratch resistance of the optical lens can be improved.
In the step 2), the hard film layer composition is prepared by the following method:
adding metal oxide particles into an ethanol water solution at room temperature, adding hydroxycyclohexane phenyl ketone, adjusting the pH to 5.5-6.5 by using a hydrochloric acid solution, stirring at a high speed for 10-30 min, then adding polyurethane resin, an organic silicon compound and an ultraviolet absorbent, continuously stirring for 5-20 min, adding a cross-linking agent, heating to 60-80 ℃, and stirring for 2-4 h to obtain the metal oxide particle.
The invention also provides the application of the optical lens in the branched optical fiber device.
By adopting the technical scheme, the optical lens is obtained by taking the polycarbonate resin as the base material, forming the hard film layer containing the polyurethane resin, the organic silicon compound, the metal oxide particles, the cross-linking agent and the ultraviolet absorbent on the base material and forming the anti-reflection film layer containing the organic silicon compound and the silicon dioxide on the hard film layer, so that the optical lens has the following beneficial effects: 1) the polyurethane resin prepared by taking the 4-aminosalicylhydrazide modified fulvic acid as the polyol has high transparency, is beneficial to improving the light transmittance and the refractive index of a final product, improves the heat resistance of an optical lens, and can improve the scratch resistance of the optical lens; 2) the right amount of hydroxycyclohexane phenyl ketone is added into the hard film layer, so that the light resistance of the optical lens can be improved, the hard film layer is not easy to yellow in the curing process, higher light transmittance and refractive index are obtained, and the heat resistance of the optical lens can be improved; 3) the surface treatment is carried out on the polycarbonate by utilizing the malic acid/oxaloacetic acid mixed solution, impurities on the surface of polyurethane are removed, a compact hard film layer is formed on the surface of the polyurethane, so that the scratch resistance of the optical lens is improved, and the adhesive force between the polycarbonate and the hard film layer can be increased.
Therefore, the optical lens comprising the plastic substrate, the hard film layer and the anti-reflection film layer provided by the invention has the advantages of good light transmission, high refractive index, good scratch resistance, excellent heat resistance, good adhesion between the plastic substrate and the hard film layer, high stability and long service life.
Drawings
FIG. 1 is an FTIR chart of 4-aminosalicylhydrazide modified fulvic acid in example 1 of the present invention; wherein a represents unmodified fulvic acid, b represents 4-aminosalicylhydrazide modified fulvic acid;
FIG. 2 is a graph showing the results of refractive index testing of an optical lens;
FIG. 3 is a graph showing the results of a light transmittance test of an optical lens;
fig. 4 is a graph showing the results of the heat resistance test of the optical lens.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
the embodiment provides 4-aminosalicylhydrazide modified fulvic acid, which is prepared by the following method:
dispersing 1 part by weight of fulvic acid into water, adjusting the pH to 11 by using a sodium hydroxide solution with the mass fraction of 20%, adding 0.6 part by weight of formaldehyde, heating to 85 ℃, adding 1.35 parts by weight of 4-aminosalicylhydrazide, heating to 95 ℃, reacting for 3.5 hours, naturally cooling to room temperature, adjusting the pH to 4.5 by using a hydrochloric acid solution with the mass fraction of 10%, heating to 100 ℃, reacting for 5 hours, and after the reaction is finished, drying at 60 ℃ to obtain the fulvic acid.
Example 2:
this example provides an optical lens prepared by the following method:
1) preparing a polyurethane resin: mixing 1 part by weight of sorbitol and 0.08 part by weight of 4-aminosalicylhydrazide modified fulvic acid obtained in example 1, introducing nitrogen, dehydrating at 105 ℃ for 2.5 hours, naturally cooling to 75 ℃, adding 0.4 part by weight of diphenylmethane diisocyanate, stirring for reaction for 2 hours at a stirring rate of 300r/min, cooling to room temperature, adding 0.04 part by weight of triethylamine, reacting for 40 minutes, adding 4 parts by weight of deionized water, stirring at a high speed for 1.5 hours at a stirring rate of 1500r/min, and finally carrying out rotary evaporation at 50 ℃ to obtain polyurethane resin;
2) pretreatment of polycarbonate resin: placing polycarbonate resin in a malic acid/oxaloacetic acid mixed solution, treating for 1h at 60 ℃, then washing with water, and drying at 90 ℃, wherein the mass fraction of oxaloacetic acid in the mixed solution is 12%, and the mass fraction of malic acid is 6%;
3) preparing a hard film layer: adding 8 parts by weight of titanium dioxide (with the average particle size of 80nm) into 200 parts by weight of ethanol aqueous solution (the mass fraction of ethanol is 40%) at room temperature, adding 1 part by weight of hydroxycyclohexane phenyl ketone, adjusting the pH to 6 by utilizing 10% by mass of hydrochloric acid solution, stirring for 20min at 1500r/min, then adding 72 parts by weight of polyurethane resin, 12 parts by weight of vinyltriethoxysilane and 2 parts by weight of phenyl o-hydroxybenzoate, continuing stirring for 10min, adding 5 parts by weight of divinylbenzene, heating to 45 ℃, stirring for 3.5h to obtain a mixed solution, coating the mixed solution on a plastic substrate, and forming a hard film layer through ultraviolet curing, wherein the thickness is 3.5 mu m, and the curing conditions are as follows: the ultraviolet illumination power is 900W, and the curing time is 20 min;
4) preparing an antireflection film layer: uniformly mixing 8 parts by weight of silicon dioxide (with an average particle size of 50nm) and 92 parts by weight of mercaptopropyltriethoxysilane, stirring to obtain a mixed solution, coating the mixed solution on a hard film layer, and forming an anti-reflection film layer through ultraviolet curing and thermocuring, wherein the thickness of the anti-reflection film layer is 0.12 mu m; the ultraviolet curing conditions are as follows: the ultraviolet illumination power is 900W, and the curing time is 10 min; the thermal curing temperature is 110 ℃, and the curing time is 2 h.
Example 3:
this example provides another optical lens, which was prepared in substantially the same manner as in example 2, except that unmodified fulvic acid was used in place of the 4-aminosalicylhydrazide-modified fulvic acid obtained in example 1 in the preparation of the polyurethane resin.
Example 4:
this example provides another optical lens, which was prepared in substantially the same manner as in example 2, except that polybutyleneadipate polyol was used instead of the 4-aminosalicylhydrazide-modified fulvic acid obtained in example 1 in the preparation of the polyurethane resin.
Example 5:
this example provides another optical lens, which is prepared in substantially the same manner as in example 2, except that the polycarbonate resin is not subjected to a pretreatment process.
Example 6:
this example provides another optical lens, which was prepared in substantially the same manner as in example 2, except that the malic acid/oxaloacetic acid mixed solution was replaced with a 12% by mass oxaloacetic acid solution during the pretreatment of the polycarbonate resin.
Example 7:
this example provides another optical lens, which was prepared in substantially the same manner as in example 2, except that the malic acid/oxaloacetic acid mixed solution was replaced with a 6% by mass malic acid solution during the pretreatment of the polycarbonate resin.
Example 8:
this example provides another optical lens, which has a preparation method substantially the same as that of example 2, except that hydroxycyclohexanone is not added in the process of preparing the hard film layer, and the specific operation steps are as follows:
adding 9 parts by weight of metal oxide particles into 500 parts by weight of ethanol aqueous solution (the mass fraction of ethanol is 40%) at room temperature, stirring for 20min at 1500r/min, then adding 72 parts by weight of polyurethane resin, 12 parts by weight of vinyltriethoxysilane and 2 parts by weight of phenyl o-hydroxybenzoate, continuing stirring for 10min, adding 5 parts by weight of divinylbenzene, heating to 45 ℃, stirring for 3.5h to obtain a mixed solution, coating the mixed solution on a plastic substrate, and forming a hard film layer through ultraviolet curing, wherein the thickness of the hard film layer is 3.5 mu m, and the curing conditions are as follows: the ultraviolet illumination power is 900W, and the curing time is 20 min;
experimental example 1:
analysis of infrared spectrogram of 4-aminosalicylhydrazide modified fulvic acid:
the test method comprises the following steps: fully drying the 4-aminosalicylhydrazide modified fulvic acid obtained in the example 1, tabletting the dried product with potassium bromide to obtain a sample, testing the sample by using a TENSOR27 type infrared spectrometer, and scanning the sample with the wave number ranging from 4000 to 500cm-1Scanning resolution of 6cm-1The number of scans was 18, and the test results are shown in fig. 1.
3400cm, as shown by curve a in FIG. 1-1Nearby absorption peaks corresponding to the O-H stretching vibration peaks of surface hydroxyl groups, bridged hydroxyl groups or adsorbed water molecules, 2920 and 2850cm-1The characteristic peak appearing nearby is the C-H stretching vibration peak on the alicyclic ring，1650cm-1The characteristic peak appeared in the vicinity of the peak was a vibration peak of C ═ C of the skeleton of the aromatic ring, 1740cm-1The characteristic peaks appeared nearby are the stretching vibration peaks of C ═ O of carboxyl and carbonyl functional groups, and the characteristic peaks are both attributed to fulvic acid; as can be seen from curve b, 3400cm-1The vibration at the position is obviously reduced, which shows that the hydrophobicity is enhanced, and the vibration is at 3230cm-1A new absorption peak which is a characteristic peak of-NH in the hydrazide group and is 1540cm appears nearby-1The characteristic peak appeared nearby belongs to the expansion vibration peak of the amide group; in conclusion, the 4-aminosalicylhydrazide modified fulvic acid is successfully prepared.
Experimental example 2:
optical performance testing of optical lenses:
refractive index: the optical lenses obtained in examples 2 to 8 were tested by using a pulfrech refractometer KPR-30 manufactured by shimadzu, and the test results are shown in fig. 2;
light transmittance: the optical lenses obtained in examples 2 to 8 were tested by using a light transmittance tester SDR4010B, and the test results are shown in fig. 3.
As shown in fig. 2 and fig. 3, the refractive index of the optical lens provided in embodiment 2 of the present invention is as high as 1.785, the light transmittance is as high as 97.6%, the refractive index is high, and the light transmittance is good; as can be seen from example 3, compared with unmodified fulvic acid, the fulvic acid obtained by using 4-aminosalicylhydrazide modified fulvic acid has higher refractive index and better light transmittance, which indicates that modification of fulvic acid by using 4-aminosalicylhydrazide with a certain mass ratio is beneficial to improvement of refractive index and light transmittance of the optical lens; as can be seen from example 8, the addition of hydroxycyclohexane phenyl ketone to the hard film layer contributes to the improvement of the refractive index and light transmittance of the optical lens; as can be seen from examples 5 to 7, the pretreatment of the plastic substrate has no significant influence on the refractive index and light transmittance of the optical lens.
Experimental example 3:
scratch resistance test of optical lenses:
the surface of the optical lens obtained in examples 2 to 8 was rubbed with steel wool 0000# 10 times at a rubbing speed of 100mm/s, and the scratch resistance was evaluated by visual observation according to the following criteria:
a: the surface of the optical lens is strongly rubbed with few scratches;
b: the surface of the optical lens is strongly rubbed to form a large number of scratches;
c: the surface of the optical lens is strongly rubbed to become opaque.
The test results are shown in table 1.
TABLE 1 scratch resistance of optical lenses
| Examples of the |
2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Scratch resistance | A | B | B | A | A | A | A |
As shown in table 1, the optical lens provided by the present invention has excellent scratch resistance, and the surface of the optical lens is strongly rubbed with almost no large number of scratches; from examples 3 and 4, it can be seen that the optical lens obtained by using the fulvic acid modified by 4-aminosalicylhydrazide has better scratch resistance compared with unmodified fulvic acid and polybutene adipate polyol, which indicates that the modification of fulvic acid by 4-aminosalicylhydrazide is helpful for improving the scratch resistance of the final product optical lens; from examples 5 to 8, it can be seen that the pretreatment of the plastic substrate and the addition of hydroxycyclohexane phenone to the hard film layer have no significant effect on the scratch resistance of the optical lens.
Experimental example 4:
adhesion test of optical lenses:
taking the optical lens having the hard film layer prepared but not the antireflection film layer prepared in examples 2 to 8 as a sample, the surface of the lens sample was scribed with a small knife in the vertical and horizontal directions at intervals of 1mm to obtain 100 squares, a cellophane tape was firmly pressed against the squares and suddenly pulled up in the vertical direction, the number of squares of the coating film remaining on the surface was counted, and the adhesiveness was evaluated according to the following criteria:
very good: 100% of squares are reserved;
o: less than 100% and not less than 95% of the squares are retained;
and (delta): less than 95% and not less than 50% of the squares are retained;
x: less than 50% of the squares remain.
The test results are shown in table 2.
TABLE 2 adhesion of optical lenses
| Examples of the |
2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Adhesive grade | ◎ | ○ | ○ | △ | ○ | ○ | ◎ |
As shown in Table 2, the optical lens provided by the invention has the advantages that the adhesion between the hard film layer and the plastic substrate is good, the hard film layer is not easy to fall off, and the service life is long; it can be seen from examples 3 and 4 that the optical lenses obtained by using the fulvic acid modified by 4-aminosalicylhydrazide have better adhesion than unmodified fulvic acid and polybutene adipate polyol; from examples 5 to 7, it can be seen that the adhesion of the optical lens can be significantly improved after the plastic substrate is pretreated by the malic acid/oxaloacetic acid mixed solution; as can be seen from example 8, the addition of hydroxycyclohexanone in the hard film layer had no significant effect on the adhesion of the optical lens.
Experimental example 5:
testing the heat resistance of the optical lens:
the optical lenses obtained in examples 2 to 8 were used as samples and tested by using a TMA-60 thermal analyzer manufactured by Shimadzu corporation, and the heat resistance thereof was evaluated by the Tg measured by the TMA penetration test method (load of 50g, tip of 0.5 mm. phi.).
The test results are shown in fig. 4.
As shown in FIG. 4, the optical lens provided by the invention has the advantages that the heat resistance temperature is as high as 138 ℃, and the heat resistance is excellent; compared with the fulvic acid which is not modified and the fulvic acid modified by 4-aminosalicylhydrazide and substituted by polybutylene adipate polyol, the optical lens obtained by using the fulvic acid modified by 4-aminosalicylhydrazide has higher heat resistance temperature and more excellent heat resistance, which shows that the modification of the fulvic acid by using a proper amount of 4-aminosalicylhydrazide is beneficial to improving the heat resistance of the final product optical lens; from example 8, it can be seen that the addition of hydroxycyclohexanone in the hard film layer can improve the heat resistance of the optical lens; as can be seen from examples 5 to 7, the pretreatment of the plastic substrate had no significant effect on the heat resistance of the optical lens.
It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the invention as set forth in the appended claims.
Claims (10)
1. The application of the polyurethane resin in preparing the optical lens is characterized in that the polyurethane resin is prepared by the reaction of sorbitol, 4-aminosalicylhydrazide modified fulvic acid and aliphatic diisocyanate.
2. The method for preparing 4-aminosalicylhydrazide modified fulvic acid as claimed in claim 1, comprising:
dispersing fulvic acid into water, adjusting the pH value to 10-12 by using a sodium hydroxide solution, adding formaldehyde, heating to 80-90 ℃, adding 4-aminosalicylhydrazide, heating to 90-100 ℃, reacting for 2-4 hours, naturally cooling to room temperature, adjusting the pH value to 4-5 by using a hydrochloric acid solution, heating to 95-100 ℃, reacting for 4-6 hours, and drying after the reaction is finished.
3. The method for producing a polyurethane resin according to claim 1, comprising:
mixing 4-aminosalicylhydrazide modified fulvic acid and sorbitol, charging nitrogen, dehydrating for 1-4 h at 100-110 ℃, naturally cooling to 70-80 ℃, adding aliphatic diisocyanate, stirring for reacting for 1-3 h, reducing the temperature to room temperature, adding triethylamine, neutralizing for reacting for 30-50 min, adding into deionized water, stirring for 1-3 h at a high speed, and finally performing rotary evaporation at 40-60 ℃ to obtain the polyurethane resin.
4. The method according to claim 3, wherein the mass ratio of the sorbitol to the 4-aminosalicylhydrazide modified fulvic acid to the aliphatic diisocyanate is 1:0.05 to 0.1:0.3 to 0.5.
5. An optical lens comprising the polyurethane resin according to claim 1.
6. An optical lens as claimed in claim 5, comprising: a plastic substrate, a hard film layer formed on the plastic substrate, and an antireflection film layer formed on the hard film layer; wherein the content of the first and second substances,
the hard film layer includes: a polyurethane resin, a silicone resin, an organosilicon compound, a crosslinking agent, an ultraviolet absorber, metal oxide fine particles, hydroxycyclohexanone, as described in claim 1;
the antireflection film layer: organosilicon compounds, silicon dioxide.
7. A method for producing an optical lens as claimed in claim 5 or 6, characterized by comprising:
1) pretreating the polycarbonate resin by using a malic acid/oxaloacetic acid mixed solution;
2) coating the hard film layer composition on a plastic substrate and forming a hard film layer through ultraviolet curing, wherein the curing conditions are as follows: the ultraviolet illumination power is 800-1000W, and the curing time is 10-30 min;
3) coating the anti-reflection film layer composition on the hard film layer and forming the anti-reflection film layer through ultraviolet curing and thermocuring; the ultraviolet curing conditions are as follows: the ultraviolet illumination power is 800-1000W, and the curing time is 5-20 min; the thermosetting temperature is 100-120 ℃, and the curing time is 1-3 h.
8. The method of claim 7, wherein the polycarbonate resin is pretreated by:
placing the polycarbonate resin in a malic acid/oxaloacetic acid mixed solution, treating for 0.5-2 h at 50-70 ℃, then washing with water, and drying at 80-100 ℃; the mass fraction of oxaloacetic acid in the mixed solution is 8-15%, and the mass fraction of malic acid is 5-10%.
9. The method of claim 7, wherein the hard film layer composition is prepared by:
adding metal oxide particles into an ethanol water solution at room temperature, adding hydroxycyclohexane phenyl ketone, adjusting the pH to 5.5-6.5 by using a hydrochloric acid solution, stirring at a high speed for 10-30 min, then adding polyurethane resin, an organic silicon compound and an ultraviolet absorbent, continuously stirring for 5-20 min, adding a cross-linking agent, heating to 60-80 ℃, and stirring for 2-4 h to obtain the metal oxide particle.
10. Use of an optical lens according to claim 5 or 6 in a bifurcated optical fibre device.
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| IL25195A (en) * | 1965-02-23 | 1970-03-22 | Montedison Spa | Dialkyl alkoyl-isomalates,their preparation and use as non-toxic plasticizers for thermoplastic vinyl resins |
| US4929828A (en) * | 1988-02-29 | 1990-05-29 | Emhart Industries, Inc. | Inspecting glass containers for line-over finish defects with bifurcated fiber optic bundle |
| JP2700290B2 (en) * | 1993-05-17 | 1998-01-19 | 三洋化成工業株式会社 | Paint composition |
| CN1103339C (en) * | 1998-08-25 | 2003-03-19 | 祝亚勤 | Prepn. method of medicinal-grade peat sodium fulvic acid |
| AU2006305319B2 (en) * | 2005-10-18 | 2012-02-09 | Jgc Catalysts And Chemicals Ltd. | Composition for use in the formation of hardcoat layer and optical lens |
| JP5831182B2 (en) * | 2011-12-01 | 2015-12-09 | 富士ゼロックス株式会社 | Transparent toner for developing electrostatic image, electrostatic image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method |
| CN103134588A (en) * | 2013-02-04 | 2013-06-05 | 杭州远方光电信息股份有限公司 | Spectrograph |
| CN103720716A (en) * | 2013-12-20 | 2014-04-16 | 广州东送能源集团有限责任公司 | Application of modified fulvic acid in preparation of antitumor drugs |
| KR101964092B1 (en) * | 2014-08-01 | 2019-04-02 | (주)엘지하우시스 | Hard coating composition containing polytetrafluoroethylene, hard coating layer and flooring including the same |
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| US20210079216A1 (en) * | 2018-05-30 | 2021-03-18 | Mitsui Chemicals, Inc. | Thermoplastic polyurethane resin, optical polyurethane resin, display panel cover plate, eyewear material, eyewear lens, eyewear frame, automobile interior/exterior component, and method for producing thermoplastic polyurethane resin |
| CN109293866B (en) * | 2018-09-21 | 2021-06-25 | 陕西科技大学 | Humic acid modified waterborne polyurethane material and preparation method thereof |
| WO2020236855A1 (en) * | 2019-05-20 | 2020-11-26 | Basf Se | Improved thermoplastic polyurethanes |
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