CN111454659A - High-refractive-index resin hardening liquid and preparation method thereof - Google Patents

High-refractive-index resin hardening liquid and preparation method thereof Download PDF

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CN111454659A
CN111454659A CN202010520823.2A CN202010520823A CN111454659A CN 111454659 A CN111454659 A CN 111454659A CN 202010520823 A CN202010520823 A CN 202010520823A CN 111454659 A CN111454659 A CN 111454659A
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refractive index
lens
hardening liquid
coupling agent
coating
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CN111454659B (en
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纪立军
张凌
王明华
张鹤军
赵毅杰
乔振安
邹永存
司云凤
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Jiangsu Shike New Material Co ltd
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Abstract

A high refractive index resin hardening liquid and a preparation method thereof, the hardening liquid includes: alcohol or ether solvent, 10-50 wt%; coupling agent, 5-30 wt%; 5-50 wt% of nano oxide particle colloid solution; 5-10 wt% of episulfide monomer and 1-5 wt% of catalyst. The hardening liquid is suitable for hardening liquid of resin substrates with the range of 1.68-1.74 high refractive indexes, can increase the surface hardness of resin lenses, and improves the film firmness between a film coating layer and the substrate, so that the lenses have the performances of wear resistance and high light transmittance.

Description

High-refractive-index resin hardening liquid and preparation method thereof
Technical Field
The invention relates to a hardening liquid which is used for manufacturing a resin surface coating with high refractive index, thereby improving the surface hardness and the friction resistance of the resin and can be used as a transition layer to connect the resin and an inorganic coating layer.
Background
The optical resin may be classified into a low refractive index (n) by dividing the refractive indexdLess than 1.56), medium refractive index (n is more than or equal to 1.56)dLess than or equal to 1.61), high refractive index of 1.61 < nd1.74 or less, and an ultrahigh refractive index of 1.74 < ndAnd the like.
These optical resins can be used to prepare ophthalmic lenses having different refractive indices. The higher the refractive index, the stronger the ability of the optical resin to condense visible light. For an optical product such as a spectacle lens which is concave or convex in nature, the smaller the curvature required, the thinner the lens, the lighter the lens, and the more comfortable and aesthetic it is to wear.
The optical resin material has disadvantages in that its surface strength is not high, and lens substrates made of various resins are easily scratched, abraded and not directly used. The current solution is to increase the surface hardness of the resin lens by immersing the resin lens substrate in a hardening liquid and dip-coating a hardening coating layer on the surface of the lens through a curing process, which is called hardening, to greatly improve the abrasion resistance of the resin lens.
The coating after curing of the hardening liquid must have a refractive index similar to that of the resin substrate it protects, otherwise it is liable to cause refraction and scattering of light at the interface between the resin substrate and the hardening layer, and thus to reduce the light transmittance of the lens, to reduce the clarity of the image formed by the lens, or to cause a photometric inaccuracy.
After the hardening liquid is formed into a film, the film can form strong interaction with the applied substrate material, a firm thin film is formed on the surface of the substrate, and the film is not easy to fall off under the conditions of substrate shrinkage or expansion caused by external force damage or temperature change.
Therefore, the composition and refractive index of the hardening liquid for protecting the lens substrates of different refractive indexes or different materials are also different. But in a certain range, the composition content of the hardening liquid can be adjusted to meet the requirements of different refractive indexes on the premise of not influencing the comprehensive performance of the hardened film layer.
The coating formed by the hardening liquid also needs to meet the requirements of the subsequent coating process. The coating process is a step of further processing a plurality of layers of inorganic substance films on the hardened resin substrate so as to further increase the surface hardness and increase the light transmittance of the lens as an antireflection layer. Because the inorganic substance film has larger property difference with the resin substrate, the hardening liquid coating is used as the intermediate transition layer, which can well play a role in connection and ensure that the coating layer can not crack and fall off.
The refractive index of the coating can be controlled by adding different components into the hardening liquid, the connection of inorganic and organic components is realized, the interaction force of the hardening liquid coating, the lens substrate and the coating layer is increased, and the sufficient adhesive force of each functional layer on the surface of the substrate is ensured. For example, organosilicon/TiO compounds can be prepared using silane coupling agents and tetrabutyl titanate2Transparent coating (organosilicon/TiO)2Property study of the clearcoat [ J]University of mansion university newspaper (nature science edition), 2011, 50 (5): 878-882.). The nano latex particles and the silane coupling agent can be mixed to prepare the hardening liquid for polymethyl methacrylate (the preparation of the waterborne organosilicon hybridization wear-resistant hardening coating for polymethyl methacrylate [ J)]Coating industry, 2016, 46 (4): 1-6.).
It can be seen that the lenses of different refractive indices are made of different materials and the corresponding hardening liquid compositions and refractive indices are different.
Although various commercial hardening liquids are commercially available at present, with the increase in the variety of resins, there is still a need for new hardening liquids suitable for various resins.
Disclosure of Invention
The invention aims to provide a hardening liquid suitable for a resin substrate with a high refractive index range of 1.68-1.74, which can increase the surface hardness of a resin lens and improve the film firmness between a film coating layer and the substrate, so that the lens has the performances of wear resistance and high light transmittance.
In order to achieve the above object, the present invention adds an episulfide monomer and a nano-oxide to a hardening liquid formulation. The nano oxide has very high refractive index and hardness, and can effectively increase the refractive index and hardness of the hardening liquid coating; the episulfide monomer has a high refractive index, and can also increase the refractive index of the hardening liquid coating. In addition, the episulfide monomer can also increase the adhesive force between the hardening liquid coating and the lens substrate, thereby avoiding the cracking and the falling off of the film layer.
The invention comprises the following technical scheme:
a high refractive index resin hardening liquid, comprising: alcohol or ether solvent, 10-50 wt%; coupling agent, 5-30 wt%; 5-50 wt% of nano oxide particle colloid solution; 5-10 wt% of episulfide monomer and 1-5 wt% of catalyst; wherein the content of the first and second substances,
the coupling agent is a silane coupling agent, a titanate coupling agent, a zirconate coupling agent and/or an aluminate coupling agent;
the catalyst is a catalyst for promoting the condensation reaction of the coupling agent;
the episulfide monomer has the general formula:
Figure BDA0002531491280000021
n is 1, 2, 3; r is C1-8 alkyl or aromatic hydrocarbon group containing 1-2 benzene rings, and the aromatic hydrocarbon group can have C1-8 alkyl substituent;
or
Figure BDA0002531491280000031
n is 1, 2, 3; r is C1-8 alkyl or aromatic hydrocarbon group containing 1-2 benzene rings, and the aromatic hydrocarbon group can have C1-8 alkyl substituent.
The high refractive index resin hardening liquid as described above, preferably, the alcohol solvent is selected from: the solvent is at least one of methanol, ethanol, propanol, butanol, isopropanol, ethylene glycol, glycerol, isobutanol, butanediol, isoprene glycol and pentaerythritol, and the ether solvent is ethylene glycol ethyl ether or ethylene glycol butyl ether.
In the high refractive index resin hardening liquid as described above, preferably, in the nano-oxide particle colloidal solution, the nano-oxide particles have a particle size in the range of 5 to 50 nm; the oxide is selected from: at least one of titanium dioxide, aluminum oxide, zirconium oxide, molybdenum oxide, and selenium oxide; the mass concentration of the nano oxide particles in the colloidal solution is 1-20%, and the solvent is ethanol or methanol.
In the high refractive index resin hardening liquid, the silane coupling agent is preferably represented by the general formula Y-R1-Si(OR2)3In the formula, Y is amino, mercapto, vinyl, epoxy, cyano, methacryloxy, methacrylate or acrylate, R1Is an alkyl group having 1 to 18 carbon atoms, OR2Is alkoxy, R2Is methyl or ethyl.
In the high refractive index resin hardening liquid, the silane coupling agent is preferably at least one selected from kh550, kh540, kh560, kh570, kh792, kh602, D L602, D L171 and 3-isocyanate triethoxysilane.
The high refractive index resin-hardened liquid as described above, preferably, the titanate coupling agent is at least one selected from the group consisting of isopropyl triisostearate, a compound of isopropyl triisostearate, isopropyldioleate acyloxy (dioctylphosphato) titanate, isopropyltris (dioctylphosphato) titanate, isopropyltrioleate acyloxy titanate, bis (dioctyloxypyrophosphate) ethylene titanate, a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, or tetraisopropylbis (dioctylphosphato) titanate.
The high refractive index resin hardening liquid as described above, preferably, the aluminate coupling agent is selected from at least one of distearoyl isopropyl aluminate, D L-411, D L-411 AF, D L-411D, D L-411 DF, anti-settling aluminate ASA, isopropoxy distearoyl acyloxy aluminate, liquid aluminate coupling agent PN-827 and triisopropoxyaluminum;
the high refractive index resin hardening liquid as described above, preferably, the zirconate coupling agent is at least one selected from the group consisting of an organic zirconate coupling agent, tetra (triethanolamine) zirconate, bis (diethyl citrate) dipropoxy zirconium chelate, sodium zirconium lactate, alkoxy tris (vinyl-ethoxy) zirconate or alkoxy tris (p-aminophenoxy) zirconate.
In the high refractive index resin hardening liquid as described above, preferably, the catalyst is at least one selected from the group consisting of formic acid, acetic acid, terephthalic acid, phthalic acid, isophthalic acid, aluminum acetylacetonate, benzenesulfonic acid, hydrochloric acid, sulfuric acid, and nitric acid.
In another aspect, the present invention provides a method for preparing the high refractive index resin hardening liquid as described above, the method comprising the steps of:
I. dissolving the coupling agent in an alcohol solvent and uniformly stirring;
II, adding the episulfide monomer into the solution obtained in the step I and uniformly stirring;
and III, adding the catalyst and the nano oxide particle colloidal solution into the mixed solution obtained in the step II, and uniformly stirring to obtain the high-refractive-index resin hardening liquid.
Titanate coupling agents used in the present invention can be roughly classified into four types according to their structures: monoalkoxy type, monoalkoxy pyrophosphate type, integral type, and ligand type.
In the hardening liquid, the nano oxide with proper content can ensure that the surface of the hardened film has higher hardness, refractive index and binding force with a coating layer; the appropriate amount of episulfide monomer can improve the film forming property, refractive index and bonding force with the base material of the hard film. The beneficial effects of the invention are as follows:
(1) the hardening liquid has high refractive index, and can be used for hardening the surface of a resin material with the refractive index of 1.68-1.74 without generating strong interface reflection, thereby obtaining high visible light transmittance.
(2) The surface coating formed by the hardening liquid has higher mechanical property and surface hardness, and can increase the surface hardness and the wear resistance of the resin material.
(3) The hardening liquid has stronger affinity with high-refractive-index optical resin materials and coating materials such as silicon dioxide, zirconium dioxide and the like, is not easy to peel off a film layer, and can be used as a transition layer to firmly bond the resin materials and the coating layer.
Drawings
FIG. 1 is a scanning electron microscope photograph of a cross section of the hardening liquid of example 9 after hardening and coating the surface of a thiourethane lens having a refractive index of 1.74.
FIG. 2 shows the cross-hatch test results of the hardening liquid of example 9 after hardening and coating the surface of a thioformate lens having a refractive index of 1.74.
Detailed Description
The present invention will be described in more detail below with reference to examples and test examples, but the present invention is not limited thereto.
The present invention will be described in detail with reference to examples and test examples.
Example 1:
1. preparation of 1 refractive index 1.68 hardening liquid
(1) Taking 300 g of methanol as a solvent, dissolving a compound of 30 g of kh560 and 20 g of isopropyl triisostearate in the methanol, and uniformly stirring;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000051
n is 3 and R is ethyl.
(3) And (3) dissolving 50 g of acetic acid, 50 g of aluminum acetylacetonate and 450 g of titanium dioxide composite colloidal ethanol solution with the average particle size of 10 nanometers and the particle mass concentration of 5 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.68, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 1
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.68 and the light transmittance was 89%. The refractive index of the lens after the hardening step was 1.68 and the light transmittance was 89%. The light transmittance of the finished product after film coating is increased to 92 percent.
Example 2:
1. preparation of a hardening liquid having a refractive index of 1.68
(1) Mixing 250 g of methanol with 50 g of ethylene glycol butyl ether as a solvent, dissolving a compound of 150 g of kh560 and 150 g of isopropyl triisostearate in the methanol, and uniformly stirring;
(2) dissolving 50 g of episulfide monomer with the structural formula shown in the following formula into 100 g of ethanol, adding the episulfide monomer into the methanol solution obtained in the step (1), and uniformly stirring;
Figure BDA0002531491280000061
n-3, and R is a quaternary carbon atom.
(3) And (3) dissolving 50 g of acetic acid and 200 g of titanium dioxide composite colloidal solution with the average particle size of 5 nanometers and the particle mass concentration of 5 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.68, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 2
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.68 and the light transmittance was 89%. The refractive index of the lens after the hardening step was 1.68 and the light transmittance was 89%. The light transmittance of the finished product after film coating is increased to 93 percent.
Example 3:
1. preparation of a hardening liquid having a refractive index of 1.68
(1) 390 g of methanol is mixed with 50 g of ethylene glycol butyl ether and 50 g of ethylene glycol ethyl ether to be used as a solvent, 30 g of kh602 and 20 g of alkoxy tri (p-aminophenoxy) zirconate are dissolved in the methanol and are stirred uniformly;
(2) dissolving 50 g of episulfide monomer with the structural formula shown in the following formula into 100 g of ethanol, adding the episulfide monomer into the methanol solution obtained in the step (1), and uniformly stirring;
Figure BDA0002531491280000071
n-3, R is hexyl.
(3) And (3) dissolving 10 g of hydrochloric acid with the molar concentration of 2M and 300 g of zirconia colloidal solution with the average particle size of 5 nanometers and the particle mass concentration of 1% into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.68, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 3
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.68 and the light transmittance was 89%. The refractive index of the lens after the hardening step was 1.68 and the light transmittance was 88%. The light transmittance of the finished product after film coating is increased to 91 percent.
Example 4:
1. preparation of a hardening liquid having a refractive index of 1.68
(1) Mixing 390 g of methanol with 50 g of ethylene glycol butyl ether and 100 g of ethylene glycol ethyl ether as solvents, dissolving 100 g of kh570 and 100 g of alkoxy tri (p-aminophenoxy) zirconate in the methanol and uniformly stirring;
(2) dissolving 100 g of episulfide monomer with the structural formula shown in the following formula into 100 g of ethanol, adding the solution into the methanol solution obtained in the step (1), and uniformly stirring;
Figure BDA0002531491280000081
n is 2 and R is n-butyl.
(3) And (3) dissolving 10 g of hydrochloric acid with the molar concentration of 2M and 50 g of zirconia colloidal solution with the average particle size of 5 nanometers and the particle mass concentration of 20 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.68, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 4
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.68 and the light transmittance was 89%. The refractive index of the lens after the hardening step was 1.68 and the light transmittance was 89%. The light transmittance of the finished product after film coating is increased to 92 percent.
Example 5:
1. preparation of a hardening liquid having a refractive index of 1.71
(1) Taking 300 g of methanol as a solvent, dissolving 50 g of kh570 and 250 g of triisostearyl isopropyl titanate (TTS) in the methanol and uniformly stirring;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000091
n is 1 and R is p-xylylene.
(3) Dissolving 50 g of terephthalic acid and 250 g of titanium dioxide/silicon dioxide composite colloidal solution with the average particle diameter of 30 nanometers and the particle mass concentration of 5 percent into the mixed solution obtained in the step (2), and uniformly stirring, wherein the mass ratio of titanium dioxide/silicon dioxide is 1: 1, obtaining a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.71, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 5
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.71 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.71 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 94 percent.
Example 6:
1. preparation of a hardening liquid having a refractive index of 1.71
(1) Taking 300 g of methanol and 200 g of isopropanol as solvents, dissolving 50 g of kh560 and 50 g of D L411 in the methanol and stirring uniformly;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000101
n-2, and R is biphenyl.
(3) And (3) dissolving 10 g of 2M sulfuric acid and 290 g of titanium dioxide colloidal solution with the average particle size of 30 nanometers and the particle mass concentration of 10 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.71, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 6
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.71 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.71 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 95 percent.
Example 7:
1. preparation of a hardening liquid having a refractive index of 1.71
(1) Taking 300 g of methanol as a solvent, dissolving 100 g of isopropyl trioleate acyloxy titanate and 100 g of D L171 in the methanol, and uniformly stirring;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000111
n-1, R is methylphenyl.
(3) And (3) dissolving 50 g of acetic acid and 350 g of molybdenum oxide colloidal solution with the average particle size of 30 nanometers and the particle mass concentration of 5% into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.71, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 7
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.71 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.71 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 95 percent.
Example 8:
1. preparation of a hardening liquid having a refractive index of 1.71
(1) Taking 500 g of methanol as a solvent, dissolving 100 g of isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate in the methanol and uniformly stirring;
(2) adding 50 g of episulfide monomer with the following structural formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000121
n-2, and R is m-xylylene.
(3) And (3) dissolving 50 g of acetic acid and 300 g of titanium dioxide colloid solution with the average particle size of 30 nanometers and the particle mass concentration of 10% into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.71, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 8
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.71 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.71 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 94 percent.
Example 9:
1. preparation of a hardening liquid having a refractive index of 1.74
(1) Taking 400 g of methanol as a solvent, dissolving 150 g of bis (dioctyloxy pyrophosphate) ethylene titanate in the methanol and uniformly stirring;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000131
n-1, and R is o-xylylene.
(3) And (3) dissolving 10 g of acetic acid, 40 g of aluminum acetylacetonate and 300 g of titanium dioxide colloid solution with the average particle size of 50 nanometers and the particle mass concentration of 20 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.74, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 9
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.74 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.74 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 94 percent.
Example 10:
1. preparation of a hardening liquid having a refractive index of 1.74
(1) Taking 450 g of methanol as a solvent, and uniformly stirring 50 g of isopropoxy distearoyl acyloxy aluminate and 50 g of alkoxy tri (p-aminophenoxy) zirconate in the methanol;
(2) adding 50 g of episulfide monomer with the following structural formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000141
n-1, and R is biphenyl.
(3) And (3) dissolving 50 g of acetic acid, 50 g of aluminum acetylacetonate, 200 g of titanium dioxide with the average particle size of 10 nanometers and the mass concentration of particles of 10 percent and 100 g of alumina colloidal solution with the average particle size of 10 nanometers and the mass concentration of particles of 10 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain the hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.74, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
Watch 10
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.74 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.74 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 94 percent.
Example 11:
1. preparation of a hardening liquid having a refractive index of 1.74
(1) Mixing 300 g of methanol with 100 g of propanol and 100 g of butanediol as solvents, dissolving 100 g of tetra (triethanolamine) zirconate and 200 g of isopropyl triisostearate in the methanol, and uniformly stirring;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000151
n-2, R is methylene diphenyl.
(3) And (3) dissolving 50 g of 2M nitric acid and 50 g of a zirconia colloidal solution with the average particle size of 10 nanometers and the particle mass concentration of 20 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.74, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 11
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.74 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.74 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 94 percent.
Example 12:
1. preparation of a hardening liquid having a refractive index of 1.74
(1) Mixing 300 g of ethanol with 50 g of isopropanol to serve as a solvent, dissolving 150 g of alkoxy tri (vinyl-ethoxy) zirconate and 150 g of isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate in methanol, and uniformly stirring;
(2) adding 100 g of episulfide monomer with the structural formula shown in the following formula into the methanol solution in the step (1) and uniformly stirring;
Figure BDA0002531491280000161
n-3, and R is a quaternary carbon atom.
(3) And (3) dissolving 50 g of acetic acid and 200 g of titanium dioxide colloid solution with the average particle size of 10 nanometers and the mass concentration of particles of 20 percent into the mixed solution obtained in the step (2), and uniformly stirring to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
(1) Adopting the hardening liquid prepared in the step 1 to harden the acrylic lens with the refractive index of 1.74, and specifically operating as follows:
i. the acrylic lens was cooled in a cooling zone in a hardening chamber for 144 seconds at a cooling temperature of 18 c and a dehumidifying temperature of 8 c.
ii, sticking and coating the cooled lens in a hardening groove at the temperature of 13 ℃;
iii, drying in three drying chambers sequentially at the temperature of 70 ℃, 70 ℃ and 68 ℃ for 432 seconds;
the dried lenses were placed in an oven and cured at 105 ℃ for 2 hours to obtain a 4 micron thick hardened layer.
(2) Coating film for hardened lens
And (3) coating the hardened lens obtained in the step (1) by using a vacuum coating machine, wherein the sequence of coating materials and the process conditions are shown in table 1, and obtaining a lens finished product with the coating thickness of 400 nanometers.
TABLE 12
Material sio2 zro2 sio2 zro2 ITO sio2 HT-100
Rate (nanometer/second) 18 5 8 5 1.5 12 2
3. Refractive index and light transmittance of lens
The refractive index of the substrate was 1.74 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.74 and the light transmittance was 90%. The light transmittance of the finished product after film coating is increased to 94 percent.
Comparative example 1
1. Preparation of a hardening liquid having a refractive index of 1.68
A hardening liquid was prepared in the same manner as in example 1 except that the step of adding an episulfide monomer was omitted, to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
The hardening and coating of the lens were carried out in the same manner as in example 1.
3. Lens performance detection
The refractive index of the substrate was 1.68 and the light transmittance was 89%. The refractive index of the lens after the hardening step was 1.70, the light transmittance was 89%, and the surface of the hardened layer became brittle. The light transmittance of the finished product after coating is increased to 91%, the refractive index of the finished product is 1.70, the finished product is higher than that of the example 1, the refractive index requirement is not met, the light transmittance is lower than that of the example 1, the film layer is easy to crack, the falling rate is more than 8%, and the firmness is poor.
Comparative example 2
1. Preparation of a hardening liquid having a refractive index of 1.71
A hardening liquid was prepared in the same manner as in example 5 except that the step of adding an episulfide monomer was omitted, to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
The lens was hardened and coated in the same manner as in example 5.
3. Lens performance detection
The refractive index of the substrate was 1.71 and the light transmittance was 90%. The refractive index of the lens after the hardening step was 1.72, the light transmittance was 89%, and the surface of the hardened layer became brittle. The light transmittance of the finished product after coating is increased to 91%, the refractive index of the finished product is 1.72, which is higher than that of the finished product in example 1, the refractive index requirement is not met, the light transmittance is lower than that of the finished product in example 1, the film layer is easy to crack, the film layer falls off by more than 10%, and the firmness is poor.
Comparative example 3
1. Preparation of a hardening liquid having a refractive index of 1.74
A hardening liquid was prepared in the same manner as in example 9 except that the step of adding an episulfide monomer was omitted, to obtain a hardening liquid product.
2. Preparation of high-refractivity and high-hardness resin lens
The hardening and coating of the lens were carried out in the same manner as in example 9.
3. Lens performance detection
The refractive index of the substrate was 1.74 and the light transmittance was 89%. The refractive index of the lens after the hardening step was 1.74, the light transmittance was 88%, and the hardened layer surface became brittle. The light transmittance of the finished product after film coating is increased to 91%, the light transmittance of the finished product is lower than that of the finished product in example 1, the film layer is easy to crack and fall off by more than 10%, and the firmness is poor.
Test example 1: and observing the hardened coating structure by a scanning electron microscope.
Taking the hardening liquid obtained in the example 9, forming a hardening layer on the surface of a 1.74 lens by a dipping method, drying the lens for 2 hours at 103 ℃, and then performing vacuum evaporation coating on the surface to obtain a finished lens. The electric conductivity of the section is increased by spraying gold in a metal ion sputtering instrument after the lens is quenched, and the section is observed under an S-4800 II field emission scanning electron microscope to be shaped, as shown in figure 1. The three-layer structure can be seen in fig. 1. With a stiffening layer in the middle and a thickness of about 4 microns. The upper layer is a coating film layer with the thickness of about 500 nanometers.
Test example 2: and testing the firmness of the film layer by a cross-cut test experiment.
The lens finished product obtained in test example 1 was subjected to film firmness test according to the national standard GB/T9286-1998 of the people's republic of China. As shown in FIG. 2, the cross-cut test results show that the affected area of the cross-cut is less than 5%, and the film firmness is qualified.
The same method is adopted to carry out film firmness test on the lens products of examples 1-8, 10-12 and comparative examples 1-3, wherein the affected area of the cross cutting positions of the films of the products of examples 1-8, 10-12 is respectively 4%, 3%, 3%, 4%, 2%, 3%, 3%, 4%, 3%, 2%, 3%, and the firmness is qualified. The affected area at the cross-cut of the lens of comparative example 1 reached 8%, which was not acceptable. The affected area at the cross-cut of the lens of comparative example 2 reached 10%, which was not acceptable. The affected area at the lens cross-cut of comparative example 3 reached 10% and failed.

Claims (10)

1. A high refractive index resin hardening liquid, comprising: alcohol or ether solvent, 10-50 wt%; coupling agent, 5-30 wt%; 5-50 wt% of nano oxide particle colloid solution; 5-10 wt% of episulfide monomer and 1-5 wt% of catalyst; wherein the content of the first and second substances,
the coupling agent is a silane coupling agent, a titanate coupling agent, a zirconate coupling agent and/or an aluminate coupling agent;
the catalyst is a catalyst for promoting the condensation reaction of the coupling agent;
the general formula of episulfide monomer is
Figure FDA0002531491270000011
n is 1, 2, 3; r is C1-8 alkyl or aromatic hydrocarbon group containing 1-2 benzene rings, and the aromatic hydrocarbon group can have C1-8 alkyl substituent;
or
Figure FDA0002531491270000012
n is 1, 2, 3; r is C1-8 alkyl or aromatic hydrocarbon group containing 1-2 benzene rings, and the aromatic hydrocarbon group can have C1-8 alkyl substituent.
2. The high refractive index resin hardening liquid according to claim 1, wherein the alcohol solvent is selected from the group consisting of: the solvent is at least one of methanol, ethanol, propanol, butanol, isopropanol, ethylene glycol, glycerol, isobutanol, butanediol, isoprene glycol and pentaerythritol, and the ether solvent is ethylene glycol ethyl ether or ethylene glycol butyl ether.
3. The high refractive index resin hardening liquid according to claim 1, wherein the nano-oxide particles in the nano-oxide particle colloidal solution have a particle diameter ranging from 5 to 50 nm; the oxide is selected from: at least one of titanium dioxide, aluminum oxide, zirconium oxide, molybdenum oxide, and selenium oxide; the mass concentration of the nano oxide particles in the colloidal solution is 1-20%, and the solvent is ethanol or methanol.
4. The high refractive index resin hardening liquid according to claim 1, wherein the silane coupling agent is represented by the general formula Y-R1-Si(OR2)3In the formula, Y is amino, mercapto, vinyl, epoxy, cyano, methacryloxy, methacrylate or acrylate, R1Is an alkyl group having 1 to 18 carbon atoms, OR2Is alkoxy, R2Is methyl or ethyl.
5. The high refractive index resin hardening liquid according to claim 1, wherein the silane coupling agent is at least one selected from kh550, kh540, kh560, kh570, kh792, kh602, D L602, D L171, and 3-isocyanate triethoxysilane.
6. The high refractive index resinated hardstock of claim 1, wherein the titanate coupling agent is selected from at least one of isopropyl triisostearate, a complex of isopropyl triisostearate, isopropyldioleate acyloxy (dioctylphosphate) titanate, isopropyltris (dioctylphosphate) titanate, isopropyltrioleate acyloxy titanate, bis (dioctyloxypyrophosphate) ethylene titanate and a chelate solution of triethanolamine or tetraisopropylbis (dioctylphosphite) titanate.
7. The high refractive index resin hardening liquid according to claim 1, wherein the aluminate coupling agent is at least one selected from the group consisting of distearoyloxy isopropyl aluminate, D L-411, D L-411 AF, D L-411D, D L-411 DF, anti-settling aluminate ASA, isopropoxy distearoyloxy aluminate, liquid aluminate coupling agent PN-827, and triisopropoxyaluminum.
8. The high refractive index resin hardening liquid according to claim 1, wherein the zirconate coupling agent is selected from at least one of organic zirconate coupling agents, tetra (triethanolamine) zirconate, bis (diethyl citrate) dipropoxy zirconium chelate, sodium zirconium lactate, alkoxy tris (vinyl-ethoxy) zirconate, or alkoxy tris (p-aminophenoxy) zirconate.
9. The high refractive index resin hardening liquid according to any one of claims 1 to 8, wherein the catalyst is at least one selected from the group consisting of formic acid, acetic acid, terephthalic acid, phthalic acid, isophthalic acid, aluminum acetylacetonate, benzenesulfonic acid, hydrochloric acid, sulfuric acid, and nitric acid.
10. The method for preparing a high refractive index resin hardening liquid according to any one of claims 1 to 9, comprising the steps of:
I. dissolving the coupling agent in an alcohol solvent and uniformly stirring;
II, adding the episulfide monomer into the solution obtained in the step I and uniformly stirring;
and III, adding the catalyst and the nano oxide particle colloidal solution into the mixed solution obtained in the step II, and uniformly stirring to obtain the high-refractive-index resin hardening liquid.
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