CN109337559A - A kind of difunctional coated optical material of anti-blue light/discoloration and preparation method thereof - Google Patents
A kind of difunctional coated optical material of anti-blue light/discoloration and preparation method thereof Download PDFInfo
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- CN109337559A CN109337559A CN201811145342.7A CN201811145342A CN109337559A CN 109337559 A CN109337559 A CN 109337559A CN 201811145342 A CN201811145342 A CN 201811145342A CN 109337559 A CN109337559 A CN 109337559A
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
A kind of difunctional coated optical material of anti-blue light/discoloration and preparation method thereof, which includes optical substrate, anti-blue light coating and photochromic coating.Polyurethane/light absorber/TiOx nano complex microsphere is adulterated in anti-blue light coating, is three layers of compound core-shell structure, and kernel is TiOx nano microballoon, and middle layer is light absorber, and shell is polyurethane.The anti-blue light coating obstructs spectral region and is extended to blue spectrum area from ultraviolet spectra area, in the case where keeping high transmittance, has the performance that absorption is distinguished to different-waveband blue light.Anti-blue light coating match with photochromic coating material and be integrated with function, can automatically adjust transmitance according to light intensity, by selectivity through beneficial to light and cut-off harmful light, realizes that light and shade is controllable, on-demand light transmission.
Description
Technical field
The invention belongs to light absorbing material technical fields, and in particular to have in 280-450nm spectral regions to different wave length
Optical material of specific absorption and preparation method thereof.
Background technique
It is well known that ultraviolet light can injure the eyes of people, in addition, the blue light in visible light can also damage eyes.
The a part of blue light as visible light has high energy, and wave-length coverage is between 400~500nm, with computer, mobile phone,
The electronic products such as ipad it is widely available, non-natural light based on blue light will generate irreversible injury to human eye, make
It is dry and astringent at human eye, tired, shed tears, myopia accelerate, macular area disease the problems such as.According to the end of the year 2009 of the World Health Organization (WHO)
Issue orange warning: blue light will be considerably beyond tonyred, melamine, the destruction of SARS etc. to potential stealthy threaten of the mankind
Property, at least 30000 people blind because of the radiation of blue light every year.Existing photochromic optical material is in optics tree mostly
Off-color material is added in rouge, preparation process is " base is anti-" technique, these materials (bright environment) in solar radiation can obstruct
The injury of ultraviolet light and strong light, but blue light cannot be obstructed at dark environment (interior), that is, change colour not anti-blue light;Human eye is to 400-
440nm range blue light depending on object and distinguishing that color is insensitive, and the wave band optical wavelength is short, energy is high, big to eye injury, for nocuousness
Blue light, optical material (device) should keep low transmission to this some blue light;440-500nm range is middle long wave blue light, to people
Eye injury is relatively small, can help pupil contraction, show the color of object, to ensure that view object picture is true beneficial to blue light
In the case where, certain transmitance is kept to this some blue light.External blue light protective materials mostly uses greatly coating technique, preparation
Technique is " film anti-" technique, i.e., absorbs blue light by blue light protecting film, and overall blue light effective percentage can only achieve 17% or so, and
The protection of short, medium and long blue spectral region cannot distinguish between;In addition, under bright environment (daylight) to obstruct strong light more difficult, human eye by
Light irradiation injury is big, i.e., anti-blue light is non-discolouring.
For from preparation process, existing photochromic " base is anti-" technique can not be simultaneous with anti-blue light " film is anti-" process matching
Hold, this is because surface blue Light Film absorbs a large amount of ultraviolet lights, so that the ultraviolet light entered in optical material matrix is reduced, and
The excitation for lacking ultraviolet light significantly reduces photochromic efficiency.Optical material technology future developing trend is the more function of development
Energy integration technology, simple function have been unable to meet the following people to integrated, the intelligent requirements of optical material and device.Cause
This, needs to absorb to spectrum line, develops high-performance intelligent optical material technology and technique, can be according to light intensity
Automatically adjust transmitance, by selectivity through beneficial to light and cut-off harmful light, realize light and shade is controllable, on-demand light transmission have it is great
Meaning.
Summary of the invention
The object of the present invention is to provide difunctional coated optical materials of a kind of anti-blue light/discoloration and preparation method thereof.Wherein
Polyurethane/light absorber/TiOx nano complex microsphere is adulterated in anti-blue light coating.The composite nano-microsphere kernel is repaired for surface
The Titanium dioxide nanoparticle of light absorber is adornd, shell cladding polyurethanes simultaneously forms compound core-shell structure.The material block
Spectral region is extended to blue spectrum area from ultraviolet spectra area, in the case where keeping high transmittance, has to different-waveband indigo plant
Light distinguishes the performance of absorption, and wherein 280-380nm ultraviolet ray transmissivity is less than 1%, 400-440nm shortwave blue light transmitance
It is more than 50% lower than 5%, 460-500nm spectral regions blue light transmitance;The anti-blue light material can with photochromic coating material into
Row matching and function are integrated, can automatically adjust transmitance according to light intensity, by selectivity through harmful beneficial to light and cut-off
Light realizes that light and shade is controllable, on-demand light transmission.It can be widely applied to automotive window, optical protection glass, LED light protecting film, preventing mobile phone
The fields such as screen, ophthalmology protective gear are protected, harmful light is solved and is injured caused by human eye.
To achieve the above object, the present invention the following technical schemes are provided:
A kind of difunctional coated optical material of anti-blue light/discoloration, including optical substrate, anti-blue light coating and photochromic painting
Layer;The photochromic coating is located at the optical substrate and first contacts ray surface, and anti-blue light coating contacts light after being located at the optical substrate
Line face;Or anti-blue light coating is located at photochromic coating and optical substrate first contacts between ray surface;
The anti-blue light coating is compound to be dispersed with polyurethane/light absorber/TiOx nano in poly- thiocarbamate
Microballoon;The weight ratio of polyurethane/light absorber/TiOx nano complex microsphere and poly- thiocarbamate is 1: (20~
200);
Polyurethane/light absorber/TiOx nano complex microsphere kernel is medium pore of titania nanosphere, middle layer
For light absorber, shell is polyurethane;The outer diameter of the complex microsphere be 8-32nm, wherein medium pore of titania nanosphere it is straight
Diameter is 3~15nm, middle layer with a thickness of 0.5~2.5nm, shell with a thickness of 2~6nm;Titanium oxide, light absorber and poly- ammonia
The weight ratio of ester is 1: (0.2~0.6): (0.2~1);
The medium pore of titania nanosphere is brilliant by monodisperse TiOx nano or crystal grain forms, the light absorber of middle layer
Particle is dispersed in surface or the hole of the medium pore of titania nanosphere.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the polyurethane is by containing two
Or the isocyanate-monomer compound of two or more isocyanate groups is polymerized with alcohol compound;
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that isocyanate-monomer compound choosing
From: toluene di-isocyanate(TDI), 4,4 '-diisocyanate of diphenyl methane-, 1,6- di-isocyanate, m-phenylenedimethylim- two
Isocyanates, naphthalene -1.5- diisocyanate, methyl cyclohexyl diisocyanate, two cyclohexyl methane diisocyanates, tetramethyl
At least one of benzene dimethylene diisocyanate and isophorone diisocyanate;
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the alcohol compound be n-butanol,
Polytetrahydrofuran ether glycol, pentaerythrite, ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, in trimethylolpropane
At least one.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the light absorber is UV absorption
Agent is selected from UV-P, UV-326, UV-327, UV-328, UV-329, UV-360, UV-531, UV-928 and quinophthalone light absorber
At least one of.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the polyurethane/light absorber/oxygen
Change titanium composite nano-microsphere to prepare with the following method:
A. Photosensitized Oxidation titanium nano material is prepared:
Sodium acetate is added into pure water, is warming up to 65-100 DEG C, after sodium acetate all dissolution, medium pore of titania is added and receives
Meter Wei Qiu is stirred 10-20 minutes, is cooled to room temperature, is separated by filtration precipitating, is washed, and ethyl alcohol is then added, and light absorption is added in stirring
Agent stands 40-100 minutes, sediment is collected by filtration after stirring 20-30 minutes, dry, obtains the oxidation of light absorber cladding
Titanium nano material;Wherein, both sodium acetate and titanium oxide mass ratio are (0.1-0.9): 1;Both light absorber and titanium oxide matter
Amount is than being (0.2-0.9): (0.5-3.0);Sodium acetate, pure water and ethyl alcohol three's mass ratio are (5-10): 100: (100-180);
B. polyurethane/light absorber/titanium oxide anti-blue light composite nano-microsphere is prepared:
Titanium dioxide nano material, the isocyanate-monomer compound of light absorber cladding prepared by step a are added to second
In acid butyl ester solvent, after mixing evenly, alcohol compound and Tween 80 are sequentially added;Wherein the titanium oxide of light absorber cladding is received
Rice material, isocyanate-monomer compound, alcohol compound, Tween 80 and butyl acetate solvent mass ratio are as follows: (0.5-1.2):
(0.4-0.9):(0.4-0.5):(1.0-2.0):(300-500);Temperature is maintained at 15-25 DEG C, stirs lower prepolymerization reaction 40-
60min obtains pre-polymer solution;Chain extender, catalyst are added in pre-polymer solution, chain extender, catalyst and isocyanic acid
Ester monomer compound three's mass ratio is (5-10): (0.2-0.5): (9-15), is heated to carrying out polymerization expansion under 45-90 DEG C of stirring
Chain reaction 10-20min generates polyurethane coating precipitating, precipitating is filtered, washed, dry, obtain polyurethane/light absorber/
Three layers of titanium oxide compound core-shell structure anti-blue light composite nano-microsphere.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the alcohol compound is n-butanol
With the mixture of polytetrahydrofuran ether glycol, n-butanol and polytetrahydrofuran ether glycol mass ratio are (1-3): (9-11);
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the chain extender is ethylene glycol;
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the catalyst is tin dilaurate two
Butyl tin;
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the sodium acetate is anhydrous sodium acetate
And sodium acetate trihydrate, preferably sodium acetate trihydrate.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the coating side of the anti-blue light coating
Method includes the following steps:
A. anti-blue light coating solution is prepared
Anti-blue light coating solution includes following three components:
(1) first component:
Polysulfide is for 60~75 parts by weight of carbamate monomer
Polyurethane/light absorber/2~9 parts by weight of TiOx nano complex microsphere
(2) second component:
Isocyanate-based 10~26 parts by weight of curing agent
(3) third components:
8~30 parts by weight of diluent
It is respectively that polysulfide is photochromic compound for carbamate monomer, polyurethane/spiro-pyrans/zinc sulphide in the ratio
Microballoon is added in container, uniform stirring 15-30 minutes at room temperature, first component is obtained, then by first component, second component and the third component
Uniformly mixing in proportion;
B. adjust viscosity with diluent, be then coated on the surface of optical substrate and form coat, by room temperature,
Light irradiation or heating make its solidification, and anti-blue light coating is made.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the coating side of the anti-blue light coating
Method includes the following steps:
I. the coating solution of first, second, the third three kinds of components is prepared;
When being II. coated with, first component, second component and the third component are uniformly mixed in proportion, is adjusted by addition diluent
Viscosity is 20~350cp under room temperature, obtains anti-blue light coating solution;
III. optical substrate pre-processes: carrying out following one or more pretreatments: alkaline aqueous solution or acid to optical substrate
Property chemistry of aqueous solution processing, milled processed, the corona treatment of different air pressures, Corona discharge Treatment, UV ozone treatment and add
Hard processing;
IV. coat: with step II prepare anti-blue light coating solution pretreated optical substrate is coated, spray or
Dip-coating forms one layer of anti-blue light coating on substrate, i.e. acquisition anti-blue light optical material;
It is highly preferred that the step IV uses dip-coating method, concrete operations are as follows: pretreated optical substrate is immersed
Into anti-blue light coating solution, impregnates 3-5 minutes, then by the slow lift-off coating solution of optical substrate, is moved in baking oven at room temperature,
Temperature is set at 35-65 DEG C, is toasted 45-90 minutes, first layer anti-blue light coating is formed;Then optical substrate is immersed in
In anti-blue light coating solution, impregnates 3-5 minutes, then by the slow lift-off coating solution of optical substrate, be moved in baking oven at room temperature, if
Temperature is set at 35-65 DEG C, is toasted 45-90 minutes, second layer anti-blue light coating is formed, obtains anti-blue light optical material.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the poly- thiocarbamate list
Body is 2,2 '-dimercaptoethylsulfides, 2,2 '-dimercapto ethylenebis dithiocarbamate ethane, 2,3- dimercapto ethylenebis dithiocarbamate propanethiol or 1,2,
At least one of 3- tri-thiol ethylenebis dithiocarbamate propane;
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the isocyanate-based curing agent is
Diisocyanate curing agent, 4,4 '-diisocyanate curing agent of diphenyl methane-, 1,6- di-isocyanate curing agent,
M-xylylene diisocyanate curing agent, methyl cyclohexyl diisocyanate curing agent and isophorone diisocyanate are solid
At least one of agent;
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the diluent be methylene chloride,
At least one in butyl acetate, methyl acetate, ethyl alcohol, butanol, acetone, toluene, dimethylbenzene, ether and polytetrahydrofuran ether glycol
Kind.
The difunctional coated optical material of anti-blue light/discoloration as described above, it is preferable that the optical substrate is optics glass
Glass, optical plastic or optical crystal, the anti-blue light coating with a thickness of 10~100 μm.
On the other hand, the present invention provides the preparation method of the difunctional coated optical material of anti-blue light/discoloration as described above,
This method can choose one of following two scheme:
Scheme one: being first coated with the anti-blue light coating solution, after being fully cured, is coated with photochromic coating;
Scheme two: label optical substrate tow sides, front is first contacts ray surface, and reverse side contacts ray surface after being, just
Face coats photochromic coating, and reverse side coats anti-blue light coating.
The photochromic coating liquid preparation of market sale can be used in photochromic coating of the present invention, or according to public
The method preparation opened, as: spiro-pyrans photochromic coating preparation method disclosed in Chinese Patent Application No. 201711110838.6.
Medium pore of titania nanosphere of the present invention can be bought with market, such as Jiangsu Huatiantong Technology Co., Ltd.
The Titanium dioxide nanoparticle of production can also be prepared according to the following method, but be not limited to following method:
Titanium tetrachloride 10mL is added dropwise in acetonitrile 95mL, generates pale yellow powder (titanium tetrachloride-to fully reacting
Acetonitrile complex intermediate) after, the deionized water of 85mL is slowly added into round-bottomed flask.Then it is heated to reflux 6-18h, with
Then the revolving speed of 4000r/min is outwelled upper liquid place the product in 30min is centrifuged in centrifuge tube, after 45 DEG C of drying, grinding is
Obtain meso-hole structure TiO2Nano-powder.
The beneficial effects of the present invention are: it is multiple that anti-blue light nanometer is adulterated in the anti-blue light coating of optical material of the present invention
Microballoon is closed, is polyurethane/compound core-shell structure of three layers of light absorber/titanium oxide, porosity nano-titanium oxide surface modification light
Absorbent, this photosensitizer processing, increases the Van der Waals region of light absorption molecule, and conjugated system increases, between different molecular
Mutually synergistic effect enhancing, photocatalytic activity enhancing, spectral response is sensitiveer, and spectral response range is from ultra-violet (UV) band to visible light
Area expands, and absorbing wavelength has dosage few, the good feature of anti-blue light effect from 410nm red shift to 450nm.By anti-blue light nanometer
Complex microsphere is doped into anti-blue light coating and prepares anti-blue light material, not will receive in optical substrates production process organic pollution and
The environmental restrictions such as high temperature.Anti-blue light material of the invention can be combined with photochromic material, realize multifunctional unit, can be according to light
Line power automatically adjusts transmitance, i.e., has the function of anti glare anti static coatings, antiultraviolet under intense light conditions, has UV resistance in the dark
The function of line, anti-blue light, light and shade is controllable, on-demand light transmission, and achieving the effect that not only can anti-blue light but also changeable colour.
Detailed description of the invention
Fig. 1 is anti-blue light coating solution abosrption spectrogram prepared by embodiment 1.
Fig. 2 is anti-blue light optical glass abosrption spectrogram prepared by embodiment 1.
Fig. 3 is the difunctional optical glass abosrption spectrogram of anti-blue light/discoloration prepared by embodiment 1.
Fig. 4 is the difunctional optical resin abosrption spectrogram of anti-blue light/discoloration prepared by embodiment 1.
Fig. 5 is titanium oxide modified Nano material transmission Electronic Speculum TEM figure prepared by embodiment 1.
Fig. 6 is polyurethane/light absorber/TiOx nano complex microsphere high-resolution-ration transmission electric-lens prepared by embodiment 1
HTEM figure.
Specific embodiment
Below by specific embodiment, the invention will be further described, but is not meant to the scope of the present invention
Limitation.
Part material source used in the following embodiment:
Nano-titanium oxide is medium pore of titania nanosphere, is purchased from Jiangsu Huatiantong Technology Co., Ltd., product type: H-
yt-30。
Photochromic coating liquid contains spiro-pyrans photochromic compound, manufacturer: Jiangsu has depending on section's new material share
Limit company, product type: SK-02.
Embodiment 1: anti-blue light composite nano-microsphere, anti-blue light coating solution, anti-blue light optical glass, anti-blue light/change are prepared
The difunctional optical glass of color and the difunctional optical resin material of anti-blue light/discoloration
(1) anti-blue light composite nano-microsphere is prepared:
1. 80g sodium acetate is added into 1000g pure water, 100 DEG C are gradually warming up to, after becoming transparent sodium acetate aqueous solution,
130g nano-titanium oxide is added, stirs 20 minutes, is cooled to room temperature, reaction solution gradually wash by layering and precipitating, solid-liquid filtration separation
Afterwards, 1500g ethyl alcohol is added, is stirred for that 50g ultraviolet absorber UV-P is added, stirs 20 minutes, stand 50 minutes, it is heavy to be collected by filtration
Starch, drying obtain titanium oxide modified Nano material;
Fig. 5 is titanium oxide modified Nano material transmission Electronic Speculum TEM figure.It can be seen that exterior appearance is spherical in shape in figure, partial size
About between 10nm, size uniformity, lattice fringe what is observed in figure is the electronic diffraction ring of sample, illustrates sample crystallization body
Well.In addition, obviously observing that Titanium particles light and shade changes in figure, this is because caused by Titanium particles are surface mesoporous.
2. taking 7g titanium oxide modified Nano material, 6.5g 1,6- di-isocyanate is added to 4000g butyl acetate solvent
In, after mixing evenly, 1.0g n-butanol, 3.5g polytetrahydrofuran ether glycol and 12g Tween 80 is added;Temperature is maintained at 20 DEG C,
Lower prepolymerization reaction 50min is stirred, 4.2g ethylene glycol, 0.1g dibutyl tin dilaurate is added, is stirred after being heated to 60 DEG C
Sediment collection is filtered, washed by 20min, dry, obtains anti-blue light composite nano-microsphere.
Fig. 6 is anti-blue light composite nano-microsphere high-resolution-ration transmission electric-lens HTEM figure.It can be seen that exterior appearance is in ball in figure
Shape, partial size about in 15nm, since polyurethane outer shell is colourless transparent material, thus are shown as white in transmission electron microscope photo
Bright circle.By Scherrer formula (D=K/ β cos θ) and Zeta potential analytical calculation, show that ultraviolet absorber and polyurethane cladding are outer
Shell average thickness is about in 2.5nm.
(2) anti-blue light coating solution is prepared:
1. configuration first component: 50g polyurethane/light absorber/TiOx nano complex microsphere is added to 650g2,3- bis-
In the thio propanethiol of mercaptoethyl (BES) monomer, uniform stirring 25min, obtains first component at room temperature;
2. configuring anti-blue light coating solution: by 180g m-xylylene diisocyanate curing agent (second component), 200g bis-
Chloromethanes (the third component) and 700g first component uniformly mix, and obtain anti-blue light coating solution.
(3) anti-blue light optical glass is prepared:
Cleaned 2mm optical fiber glass substrate two sides is carried out A and B to mark, wherein the face A is first to contact ray surface, B
Face contacts ray surface after being, sprays above-mentioned anti-blue light coating solution to the face optical fiber glass substrate B, after spraying, moves in baking oven,
Temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature after placing 24 hours, repeats second of progress and sprays
It applies, after being fully cured, obtains anti-blue light optical material, anti-blue light coating layer thickness is 42 μm.
(4) the difunctional optical glass of anti-blue light/discoloration is prepared:
The above-mentioned face anti-blue light optical material A is subjected to the spraying of photochromic coating liquid, after spraying, is moved in baking oven,
Temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeats to spray a photochromic coating liquid, after being fully cured, be had
There are anti-blue light and discoloration dual function optical glass.Photochromic coating is with a thickness of 43 μm.
(5) the difunctional optical resin material of anti-blue light/discoloration is prepared:
The anti-blue light composite nano-microsphere 2.3g for taking step (1) to prepare is added to 100ml m-phenylenedimethylim- diisocyanate
In ester (XDI), after twenty minutes, 2,3- dimercapto ethylenebis dithiocarbamate propanethiol 85ml is added in uniform stirring, is mixed;3.6g is added
Dibutyl tin dilaurate (DBTL) catalyst, then by said mixture, prepolymerization 45 minutes, filtering vacuum are de- at 65 DEG C
Raw material is poured into mold after bubble, raw material is raised to 120 DEG C according to program curing and is solidified 18 hours, room temperature is cooled to, is demoulded
The polyurethane optical sheet of doping anti-blue light composite nano-microsphere is obtained after cleaning.
Photochromic coating liquid is sprayed to contact ray surface polyurethane optical sheet at first, after spraying, moves to baking oven
In, temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeats to spray a photochromic coating liquid, after being fully cured, obtain
To with anti-blue light and discoloration dual function optical resin material.Photochromic coating is with a thickness of 40 μm.
Comparative example 1: the difunctional optical resin material of anti-blue light/discoloration of preparation doping UV- titanium oxide (is received without anti-blue light
Rice complex microsphere)
2.3g nano-titanium oxide is taken to be added in 100ml m-xylylene diisocyanate (XDI), uniform stirring 20 divides
2,3- dimercapto ethylenebis dithiocarbamate propanethiol 85ml is added in Zhong Hou, and 1.85g ultraviolet absorber UV-P is added, and is mixed;It is added
3.6g dibutyl tin dilaurate (DBTL) catalyst, then by said mixture, prepolymerization 45 minutes, filtering are true at 65 DEG C
After empty deaeration, raw material is poured into mold, raw material is raised to 120 DEG C according to program curing and is solidified 18 hours, room temperature is cooled to,
After demoulding cleaning, the polyurethane optical sheet of doping UV- titanium oxide is obtained.To contact ray surface polyurethane optical sheet spray at first
Photochromic coating liquid is applied, after spraying, is moved in baking oven, temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeat
A photochromic coating liquid is sprayed, after being fully cured, is obtained with anti-blue light and discoloration dual function optical resin material.Light
Mutagens color coating layer thickness is 43 μm.
Comparative example 2: optical resin material (be free of titanium oxide) of the preparation containing ultraviolet absorber
100ml m-xylylene diisocyanate (XDI) is added to 85ml 2,3- dimercapto ethylenebis dithiocarbamate propanethiol
In, 1.85g ultraviolet absorber UV-P is added, is mixed;3.6g dibutyl tin dilaurate (DBTL) catalyst is added, then
By said mixture, raw material is poured into mold by prepolymerization 45 minutes after filtering vacuum deaeration at 65 DEG C, according to solidification path
Raw material is raised to 120 DEG C and solidified 18 hours by sequence, is cooled to room temperature and is obtained the polyurethane light containing ultraviolet absorber after demoulding cleaning
Learn sheet material;Photochromic coating liquid is sprayed to contact ray surface polyurethane optical sheet at first, after spraying, moves to baking oven
In, temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeats to spray a photochromic coating liquid, after being fully cured, obtain
To the optical resin material containing ultraviolet absorber.Photochromic coating is with a thickness of 43 μm.
Comparative example 3: optical resin material (be free of ultraviolet absorber) of the preparation containing nano oxidized titanium particle
2.3g nano-titanium oxide is taken to be added in 100ml m-xylylene diisocyanate (XDI), uniform stirring 20 divides
2,3- dimercapto ethylenebis dithiocarbamate propanethiol 85ml is added in Zhong Hou, is mixed;It is added 3.6g dibutyl tin dilaurate (DBTL)
Catalyst, then by said mixture at 65 DEG C prepolymerization 45 minutes, after filtering vacuum deaeration, raw material is poured into mold
In, raw material is raised to 120 DEG C according to program curing and is solidified 18 hours, room temperature is cooled to and obtains adulterated TiOx after demoulding cleaning
Polyurethane optical sheet;Photochromic coating liquid is sprayed to contact ray surface polyurethane optical sheet at first, after spraying,
It moves in baking oven, temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeat to spray a photochromic coating liquid, it is completely solid
After change, the optical resin material of titanium oxide contained nanometer particle is obtained.Photochromic coating is with a thickness of 40 μm.
Embodiment 2: anti-blue light composite nano-microsphere, anti-blue light coating solution, anti-blue light optical glass, anti-blue light/change are prepared
The difunctional optical glass of color and the difunctional optical resin material of anti-blue light/discoloration
(1) anti-blue light composite nano-microsphere is prepared:
95g sodium acetate is added into 1000g pure water, is gradually warming up to 100 DEG C, after becoming transparent sodium acetate aqueous solution, adds
Enter 180g nano-titanium oxide, stir 20 minutes, be cooled to room temperature, reaction solution gradually wash by layering and precipitating, solid-liquid filtration separation
Afterwards, it after 1700g ethyl alcohol being added, is stirred for that 36g ultraviolet absorber UV-P is added, stirs 25 minutes, stand 50 minutes, be collected by filtration
Sediment, drying obtain titanium oxide modified Nano material;
7g titanium oxide modified Nano material, 4.2g isophorone diisocyanate is taken to be added to 3500g butyl acetate solvent
In, after mixing evenly, 1.0g n-butanol, 3.5g polytetrahydrofuran ether glycol and 12g Tween 80 is added;Temperature is maintained at 25 DEG C,
Lower prepolymerization reaction 50min is stirred, 2.7g ethylene glycol, 0.1g dibutyl tin dilaurate is added, is stirred after being heated to 60 DEG C
Sediment collection is filtered, washed by 20min, dry, obtains anti-blue light composite nano-microsphere.
(2) anti-blue light coating solution is prepared:
1. configuration first component: 50g polyurethane/light absorber/TiOx nano complex microsphere is added to 350g 2,3- bis-
In the thio propanethiol of mercaptoethyl (BES) monomer, uniform stirring 25min, obtains first component at room temperature;
2. configuring anti-blue light coating solution: by 120g m-xylylene diisocyanate curing agent (second component), 100g bis-
Chloromethanes (the third component) and 400g first component uniformly mix, and obtain anti-blue light coating solution.
(3) anti-blue light optical glass is prepared:
Cleaned 2mm optical fiber glass substrate two sides is carried out A and B to mark, wherein the face A is first to contact ray surface, B
Face contacts ray surface after being, sprays above-mentioned anti-blue light coating solution to the face optical fiber glass substrate B, after spraying, moves in baking oven,
Temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature after placing 24 hours, repeats second of progress and sprays
It applies, after being fully cured, obtains anti-blue light optical material, anti-blue light coating layer thickness is 40 μm.
(4) the difunctional optical glass of anti-blue light/discoloration is prepared:
The anti-blue light face optical material A of step (3) preparation is subjected to the spraying of photochromic coating liquid, after spraying, is moved
Into baking oven, temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeats to spray a photochromic coating liquid, be fully cured
Afterwards, it obtains with anti-blue light and discoloration dual function optical material.Photochromic coating is with a thickness of 45 μm.
(5) the difunctional optical resin material of anti-blue light/discoloration is prepared:
Cleaned 2mm polyurethane optical substrate two sides is carried out A and B to mark, wherein the face A is first to contact light
Face, the face B contact ray surface after being, spray photochromic coating liquid to the face optical substrate A respectively, and the face B sprays above-mentioned anti-blue light and applies
Layer liquid, after spraying, moves in baking oven, and temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature places 24
After hour, repeats second of progress and spray, after being fully cured, obtain the difunctional optical resin material of anti-blue light/discoloration.Anti- indigo plant
Light coating is with a thickness of 45 μm, and photochromic coating is with a thickness of 42 μm.
Embodiment 3: anti-blue light composite nano-microsphere, anti-blue light coating solution, anti-blue light optical glass, anti-blue light/change are prepared
The difunctional optical glass of color and the difunctional optical resin material of anti-blue light/discoloration
(1) anti-blue light composite nano-microsphere is prepared:
75g sodium acetate is added into 1000g pure water, is gradually warming up to 100 DEG C, after becoming transparent sodium acetate aqueous solution, adds
Enter 100g nano-titanium oxide, stir 20 minutes, be cooled to room temperature, reaction solution gradually wash by layering and precipitating, solid-liquid filtration separation
Afterwards, it after 1300g ethyl alcohol being added, is stirred for that 28g ultraviolet absorber UV-P is added, stirs 20 minutes, stand 50 minutes, be collected by filtration
Sediment, drying obtain titanium oxide modified Nano material;
Take that 7g titanium oxide modified Nano material, that 7g m-xylylene diisocyanate is added to 4000g butyl acetate is molten
In agent, after mixing evenly, 1.0g n-butanol, 3.5g polytetrahydrofuran ether glycol and 15g Tween 80 is added;Temperature is maintained at 20
DEG C, lower prepolymerization reaction 50min is stirred, 4.2g ethylene glycol, 0.15g dibutyl tin dilaurate is added, is stirred after being heated to 55 DEG C
20min is mixed, sediment collection is filtered, washed, it is dry, obtain anti-blue light composite nano-microsphere.
(2) anti-blue light coating solution is prepared:
1. configuration first component: 50g polyurethane/light absorber/TiOx nano complex microsphere is added to 850g2,3- bis-
In the thio propanethiol of mercaptoethyl (BES) monomer, uniform stirring 25min, obtains first component at room temperature;
2. configuring anti-blue light coating solution: by 250g m-xylylene diisocyanate curing agent (second component), 230g bis-
Chloromethanes (the third component) and 900g first component uniformly mix, and obtain anti-blue light coating solution.
(3) anti-blue light optical glass is prepared:
Cleaned 2mm optical fiber glass substrate two sides is sprayed above-mentioned anti-blue light coating solution, after spraying, is moved to
In baking oven, temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature obtains anti-blue light light after placing 24 hours
Learn material.Single side anti-blue light coating with a thickness of 42 μm.
(4) the difunctional optical glass of anti-blue light/discoloration is prepared:
Cleaned 2mm optical fiber glass substrate is contacted ray surface at first and sprays above-mentioned anti-blue light coating solution, spraying
After, it moves in baking oven, temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature obtains after placing 24 hours
To first layer anti-blue light coating;Then second layer photochromic coating is sprayed on first layer anti-blue light coating, after spraying,
It moves in baking oven, temperature is set at 45 DEG C, is toasted 80 minutes;It repeats to spray a photochromic coating liquid, after being fully cured, obtain
To with anti-blue light and discoloration dual function optical glass.Anti-blue light coating with a thickness of 42 μm, photochromic coating with a thickness of
42μm。
(5) the difunctional optical resin material of anti-blue light/discoloration is prepared:
Cleaned 2mm polyurethane optical substrate two sides is carried out A and B to mark, wherein the face A is first to contact light
Face, the face B contact ray surface after being, spray photochromic coating liquid to the face optical substrate A respectively, and the face B sprays above-mentioned anti-blue light and applies
Layer liquid, after spraying, moves in baking oven, and temperature setting is at 50 DEG C, and after baking 90 minutes, slow cooling to room temperature places 20
After hour, repeats second of progress and spray, after being fully cured, obtain the difunctional optical resin material of anti-blue light/discoloration.Anti- indigo plant
Light coating is with a thickness of 44 μm, and photochromic coating is with a thickness of 40 μm.
Embodiment 4: anti-blue light composite nano-microsphere, anti-blue light coating solution, anti-blue light optical glass, anti-blue light/change are prepared
The difunctional optical glass of color and the difunctional optical resin material of anti-blue light/discoloration
(1) anti-blue light composite nano-microsphere is prepared:
85g sodium acetate is added into 1000g pure water, is gradually warming up to 100 DEG C, after becoming transparent sodium acetate aqueous solution, adds
Enter 155g nano-titanium oxide, stir 20 minutes, be cooled to room temperature, reaction solution gradually wash by layering and precipitating, solid-liquid filtration separation
Afterwards, it after 1600g ethyl alcohol being added, is stirred for that 45g ultraviolet absorber UV-P is added, stirs 20 minutes, stand 50 minutes, be collected by filtration
Sediment, drying obtain titanium oxide modified Nano material;
7g titanium oxide modified Nano material, 5g isophorone diisocyanate is taken to be added in 3600g butyl acetate solvent,
After mixing evenly, 1.0g n-butanol, 3g polytetrahydrofuran ether glycol and 12g Tween 80 is added;Temperature is maintained at 18 DEG C, under stirring
Prepolymerization reaction 50min adds 3g ethylene glycol, 0.1g dibutyl tin dilaurate, stirs 20min after being heated to 60 DEG C, will sink
Starch collection is filtered, washed, dry, obtains anti-blue light composite nano-microsphere.
(2) anti-blue light coating solution is prepared:
1. configuration first component: 50g polyurethane/light absorber/TiOx nano complex microsphere is added to 450g 2,3- bis-
In the thio propanethiol of mercaptoethyl (BES) monomer, uniform stirring 25min, obtains first component at room temperature;
2. configuring anti-blue light coating solution: by 150g m-xylylene diisocyanate curing agent (second component), 160g bis-
Chloromethanes (the third component) and 500g first component uniformly mix, and obtain anti-blue light coating solution.
(3) anti-blue light optical glass is prepared:
Cleaned 2mm optical fiber glass substrate two sides is sprayed above-mentioned anti-blue light coating solution, after spraying, is moved to
In baking oven, temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature obtains anti-blue light light after placing 24 hours
Learn material.Single side anti-blue light coating with a thickness of 42 μm.
(4) the difunctional optical glass of anti-blue light/discoloration is prepared:
Cleaned 2mm optical fiber glass substrate is contacted ray surface at first and sprays above-mentioned anti-blue light coating solution, spraying
After, it moves in baking oven, temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature obtains after placing 24 hours
To first layer anti-blue light coating;Then second layer photochromic coating is sprayed on first layer anti-blue light coating, after spraying,
It moves in baking oven, temperature is set at 45 DEG C, is toasted 80 minutes;It repeats to spray a photochromic coating liquid, after being fully cured, obtain
To with anti-blue light and discoloration dual function optical glass.Anti-blue light coating with a thickness of 43 μm, photochromic coating with a thickness of
45μm。
(5) the difunctional optical resin material of anti-blue light/discoloration is prepared:
The anti-blue light composite nano-microsphere 2.5g for taking step (1) to prepare is added to 100ml m-phenylenedimethylim- diisocyanate
In ester (XDI), after twenty minutes, 2,3- dimercapto ethylenebis dithiocarbamate propanethiol 70ml is added in uniform stirring, is mixed;3.2g is added
Dibutyl tin dilaurate (DBTL) catalyst, then by said mixture, prepolymerization 45 minutes, filtering vacuum are de- at 65 DEG C
After bubble, raw material is poured into mold, raw material is raised to 120 DEG C according to program curing and is solidified 20 hours, room temperature is cooled to, is demoulded
The polyurethane optical sheet that doping anti-blue light composite nano-microsphere is obtained after cleaning, to contact ray surface polyurethane optical sheet at first
Material sprays photochromic coating liquid, after spraying, moves in baking oven, and temperature is arranged at 45 DEG C, toasts 80 minutes;After solidification,
It repeats to spray a photochromic coating liquid, after being fully cured, obtain with anti-blue light and discoloration dual function optical resin material
Material.Photochromic coating is with a thickness of 43 μm.
Embodiment 5: anti-blue light composite nano-microsphere, anti-blue light coating solution, anti-blue light optical glass, anti-blue light/change are prepared
The difunctional optical glass of color and the difunctional optical resin material of anti-blue light/discoloration
(1) anti-blue light composite nano-microsphere is prepared:
65g sodium acetate is added into 1000g pure water, is gradually warming up to 100 DEG C, after becoming transparent sodium acetate aqueous solution, adds
Enter 100g nano-titanium oxide, stir 20 minutes, be cooled to room temperature, reaction solution gradually wash by layering and precipitating, solid-liquid filtration separation
Afterwards, it after 1200g ethyl alcohol being added, is stirred for that 15g ultraviolet absorber UV-P is added, stirs 20 minutes, stand 50 minutes, be collected by filtration
Sediment, drying obtain titanium oxide modified Nano material;
7g titanium oxide modified Nano material, 8.4g 1 are taken, 6- di-isocyanate is added to 4500g butyl acetate solvent
In, after mixing evenly, 1.0g n-butanol, 3.5g polytetrahydrofuran ether glycol and 18g Tween 80 is added;Temperature is maintained at 22 DEG C,
Lower prepolymerization reaction 50min is stirred, 5g ethylene glycol, 0.15g dibutyl tin dilaurate is added, is stirred after being heated to 55 DEG C
Sediment collection is filtered, washed by 20min, dry, obtains anti-blue light composite nano-microsphere.
(2) anti-blue light coating solution is prepared:
1. configuration first component: 50g polyurethane/light absorber/TiOx nano complex microsphere is added to 1150g 2,3-
In dimercapto ethylenebis dithiocarbamate propanethiol (BES) monomer, uniform stirring 25min, obtains first component at room temperature;
2. configuring anti-blue light coating solution: by 260g m-xylylene diisocyanate curing agent (second component), 250g bis-
Chloromethanes (the third component) and 1200g first component uniformly mix, and obtain anti-blue light coating solution.
(3) anti-blue light optical glass is prepared:
Cleaned 2mm optical fiber glass substrate two sides is carried out A and B to mark, wherein the face A is first to contact ray surface, B
Face contacts ray surface after being, sprays above-mentioned anti-blue light coating solution to the face optical fiber glass substrate B, after spraying, moves in baking oven,
Temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature after placing 24 hours, repeats second of progress and sprays
It applies, after being fully cured, obtains anti-blue light optical material, anti-blue light coating layer thickness is 42 μm.
(4) the difunctional optical glass of anti-blue light/discoloration is prepared:
The above-mentioned face anti-blue light optical material A is subjected to the spraying of photochromic coating liquid, after spraying, is moved in baking oven,
Temperature is set at 45 DEG C, is toasted 80 minutes;After solidification, repeats to spray a photochromic coating liquid, after being fully cured, be had
There are anti-blue light and discoloration dual function optical material.Photochromic coating is with a thickness of 43 μm.
(5) the difunctional optical resin material of anti-blue light/discoloration is prepared:
Cleaned 2mm optical resin substrate is contacted ray surface at first and sprays above-mentioned anti-blue light coating solution, spraying
After, it moves in baking oven, temperature setting is at 50 DEG C, and after baking 100 minutes, slow cooling to room temperature obtains after placing 24 hours
To first layer anti-blue light coating, repeat to spray primary;Then photochromic coating liquid is sprayed on anti-blue light coating, spraying terminates
Afterwards, it moves in baking oven, temperature is set at 45 DEG C, is toasted 80 minutes;It repeats to spray a photochromic coating liquid, be fully cured
Afterwards, it obtains with anti-blue light and discoloration dual function optical resin material.Anti-blue light coating layer thickness is 42 μm, photochromic coating
With a thickness of 43 μm.
Embodiment 6: optical property test experience
Light transmission rate (T/%) performance detection is carried out respectively to the anti-blue light coating solution of embodiment 1-5 preparation, wherein penetrating
Shanghai Yuan Xi Instrument Ltd. UV-8000 type ultraviolet-visible photometer is selected in rate detection;Detection method: directly by anti-blue light
Coating solution is coated on the photometric prism of ultraviolet-visible and measures light transmittance, and wherein detection numerical value in ultraviolet spectra area chooses 280-
380nm Range Mean, blue spectrum area selects respectively at 440nm, numerical value is detected at 460nm and at 480nm;Visible range
It selects as detection numerical value at 680nm, testing result is listed in table one.Fig. 1 is that anti-blue light coating solution prepared by embodiment 1 absorbs light
Spectrogram.
One anti-blue light coating solution light transmission rate detection case list position of table: T%
Embodiment 7: anti-blue light glass optics properties detection
Light transmission rate (T/%) performance detection is carried out to the anti-blue light glass of embodiment 1-5 preparation respectively, selects Shanghai member
Instrument Ltd. UV-8000 type ultraviolet-visible photometer is analysed, wave-length coverage is the visible region and wavelength of 400~780nm
Range is the ultraviolet region of 200~400nm, the light source using different illuminators as instrument.Testing result is listed in table two.Figure
The 2 anti-blue light optical glass abosrption spectrograms prepared for embodiment 1.
Two anti-blue light optical glass light transmission rate detection case list position of table: T%
Embodiment 8: the difunctional optical material optical property detection of anti-blue light/discoloration
The difunctional optical glass of anti-blue light/discoloration and bifunctional resin sheet material prepared by embodiment 1-5 and comparative example 1-3
Light transmission rate (T/%) performance and the detection of photochromic response are carried out respectively.Select Shanghai Yuan Xi Instrument Ltd. UV-
The double light photometers of 8000 type ultraviolet-visibles, the visible region and wave-length coverage that wave-length coverage is 400~780nm be 200~
The ultraviolet region of 400nm, the light source using different illuminators as instrument.Photochromic response is being taken off using sample
Ratio between luminous transmittance τ v (0) under color state and the luminous transmittance τ v (15) after 15min illumination under color change state,
That is: τ v (0)/τ v (15).After solar simulator radiation intensity irradiating sample 30min, test sample visible light transmittance.Inspection
Survey method: use solar simulator standard sources, solar simulator select 1000W deuterium lamp, illumination be (50+5) ×
103Sample is directly mounted between detector and light source by 1x, after centralized positioning, irradiates sample with light source, together
When, irradiating sample after solar simulator radiation intensity is reduced to 30%, temperature setting is 25 DEG C, to determine sample medium
Photochromic response under illuminance.Complete bleached state optical property detection: sample is placed in dark environment 60 minutes
Afterwards, then other optical property detections are carried out, wherein it is flat to choose 280-380nm spectral region light transmittance for detection numerical value in ultraviolet spectra area
Mean value;It detects numerical value and chooses 380-440nm spectral region light transmittance peak in blue spectrum area;Detect numerical value choosing in visible range
Take 600-780nm spectral region light transmittance minimum.Testing result is listed in table three, table four.Fig. 3 is anti-indigo plant prepared by embodiment 1
The difunctional optical glass abosrption spectrogram of light/discoloration.Fig. 4 is that the difunctional optical resin of anti-blue light/discoloration prepared by embodiment 1 is inhaled
Receive spectrogram.
Three sample color change state performance detection situation table of table
Four Sample Fade state light transmission rate detection case list position of table: T%
It was found from above-mentioned testing result: of the invention anti-containing polyurethane/light absorber/TiOx nano complex microsphere
Blue light optical material increases in the absorption spectrum Einstein shift amount of ultraviolet visible light region, harmful spectral absorptive capacity enhancing, wherein 280-
Transmitance≤0.1%, 380-440nm blue spectrum area of 380nm ultraviolet spectra area transmitance≤5.5%, 480nm blue light transmitance
The visible range >=70%, 600-780nm transmitance >=80%;Meanwhile this anti-blue light optical material can be with photochromic material
Material carry out function combination of sets at, can according to light intensity automatically adjust transmitance, in light and shade varying environment, all have absorption not
The function of co-wavelength spectrum, photochromic response >=1.85, bleached state 380-440nm anti-blue light performance is stronger, preferably
Solves harmful light injury caused by human eye.
Claims (10)
1. a kind of difunctional coated optical material of anti-blue light/discoloration, which is characterized in that it includes optical substrate, anti-blue light coating
And photochromic coating;The photochromic coating is located at the optical substrate and first contacts ray surface, and anti-blue light coating is located at the optics
Ray surface is contacted after substrate;Or anti-blue light coating is located at photochromic coating and optical substrate first contacts between ray surface;
The anti-blue light coating is to be dispersed with polyurethane/light absorber/TiOx nano complex microsphere in poly- thiocarbamate;
The weight ratio of polyurethane/light absorber/TiOx nano complex microsphere and poly- thiocarbamate is 1: (20~200);
Polyurethane/light absorber/TiOx nano complex microsphere kernel is medium pore of titania nanosphere, and middle layer is light
Absorbent, shell are polyurethane;The outer diameter of the complex microsphere is 8-32nm, wherein the diameter of medium pore of titania nanosphere is 3
~15nm, middle layer with a thickness of 0.5~2.5nm, shell with a thickness of 2~6nm;Titanium oxide, light absorber and polyurethane
Weight ratio is 1: (0.2~0.6): (0.2~1);
The medium pore of titania nanosphere is brilliant by monodisperse TiOx nano or crystal grain forms, the light absorber particle of middle layer
It is dispersed in surface or the hole of the medium pore of titania nanosphere.
2. the difunctional coated optical material of anti-blue light/discoloration as described in claim 1, which is characterized in that the polyurethane is
It is polymerized by the isocyanate-monomer compound of the isocyanate groups containing two or two or more with alcohol compound;
Preferably, which is selected from: toluene di-isocyanate(TDI), 4,4 '-diisocyanate of diphenyl methane-
Ester, 1,6- di-isocyanate, m-xylylene diisocyanate, naphthalene -1.5- diisocyanate, two isocyanide of methyl cyclohexyl
In acid esters, two cyclohexyl methane diisocyanates, tetramethylxylylene diisocyanate and isophorone diisocyanate
At least one;
Preferably, which is n-butanol, polytetrahydrofuran ether glycol, pentaerythrite, ethylene glycol, propylene glycol, fourth two
At least one of alcohol, hexylene glycol, neopentyl glycol, trimethylolpropane.
3. the difunctional coated optical material of anti-blue light/discoloration as described in claim 1, which is characterized in that the light absorber
For ultraviolet absorber, it is selected from UV-P, UV-326, UV-327, UV-328, UV-329, UV-360, UV-531, UV-928 and quinoline phthalein
At least one of ketone light absorber.
4. the difunctional coated optical material of anti-blue light/discoloration as described in claim 1, which is characterized in that the polyurethane/light
Absorbent/TiOx nano complex microsphere is prepared with the following method:
A. Photosensitized Oxidation titanium nano material is prepared:
Sodium acetate is added into pure water, is warming up to 65-100 DEG C, after sodium acetate all dissolution, it is micro- that medium pore of titania nanometer is added
Ball stirs 10-20 minutes, is cooled to room temperature, is separated by filtration precipitating, washs, and ethyl alcohol is then added, and light absorber is added in stirring,
After stirring 20-30 minutes, 40-100 minutes are stood, sediment is collected by filtration, dry, the titanium oxide for obtaining light absorber cladding is received
Rice material;Wherein, both sodium acetate and titanium oxide mass ratio are (0.1-0.9): 1;Both light absorber and titanium oxide mass ratio
For (0.2-0.9): (0.5-3.0);Sodium acetate, pure water and ethyl alcohol three's mass ratio are (5-10): 100: (100-180);
B. polyurethane/light absorber/titanium oxide anti-blue light composite nano-microsphere is prepared:
Titanium dioxide nano material, the isocyanate-monomer compound of light absorber cladding prepared by step a are added to acetic acid fourth
In ester solvent, after mixing evenly, alcohol compound and Tween 80 are sequentially added;The wherein TiOx nano material of light absorber cladding
Material, isocyanate-monomer compound, alcohol compound, Tween 80 and butyl acetate solvent mass ratio are as follows: (0.5-1.2): (0.4-
0.9):(0.4-0.5):(1.0-2.0):(300-500);Temperature is maintained at 15-25 DEG C, stirs lower prepolymerization reaction 40-60min,
Obtain pre-polymer solution;Chain extender, catalyst are added in pre-polymer solution, chain extender, catalyst and isocyanate-monomer
Compound three's mass ratio is (5-10): (0.2-0.5): (9-15), is heated to carrying out polymerization chain extending reaction under 45-90 DEG C of stirring
10-20min generates polyurethane coating precipitating, precipitating is filtered, washed, dry, obtains polyurethane/light absorber/titanium oxide
Three layers of compound core-shell structure anti-blue light composite nano-microsphere.
5. the difunctional coated optical material of anti-blue light/discoloration as claimed in claim 4, which is characterized in that the alcohols chemical combination
Object is the mixture of n-butanol and polytetrahydrofuran ether glycol, and n-butanol and polytetrahydrofuran ether glycol mass ratio are (1-3):
(9-11);
Preferably, the chain extender is ethylene glycol;
Preferably, the catalyst is dibutyl tin dilaurate;
Preferably, the sodium acetate is anhydrous sodium acetate and sodium acetate trihydrate, preferably sodium acetate trihydrate.
6. the difunctional coated optical material of anti-blue light/discoloration according to any one of claims 1 to 5, which is characterized in that institute
The coating method for stating anti-blue light coating includes the following steps:
A. anti-blue light coating solution is prepared
Anti-blue light coating solution includes following three components:
(1) first component:
Polysulfide is for 60~75 parts by weight of carbamate monomer
Polyurethane/light absorber/2~9 parts by weight of TiOx nano complex microsphere
(2) second component:
Isocyanate-based 10~26 parts by weight of curing agent
(3) third components:
8~30 parts by weight of diluent
In the ratio respectively by polysulfide for carbamate monomer, the polyurethane/photochromic complex microsphere of spiro-pyrans/zinc sulphide
Be added container in, uniform stirring 15-30 minute at room temperature, obtain first component, then by first component, second component and the third component by than
Example uniformly mixing;
B. viscosity is adjusted with diluent, is then coated on the surface of optical substrate and forms coat, passes through room temperature, illumination
Penetrating or heating makes its solidification, and anti-blue light coating is made.
7. the difunctional coated optical material of anti-blue light/discoloration as claimed in claim 6, which is characterized in that the anti-blue light applies
The coating method of layer includes the following steps:
I. the coating solution of first, second, the third three kinds of components is prepared;
When being II. coated with, first component, second component and the third component are uniformly mixed in proportion, viscosity is adjusted by addition diluent
For 20~350cp under room temperature, anti-blue light coating solution is obtained;
III. optical substrate pre-processes: carrying out following one or more pretreatments: alkaline aqueous solution or acid water to optical substrate
At solution chemistry processing, milled processed, the corona treatment of different air pressures, Corona discharge Treatment, UV ozone treatment and stiffened
Reason;
IV. it coats: pretreated optical substrate being coated, sprayed or soaked with anti-blue light coating solution prepared by step II
It applies, forms one layer of anti-blue light coating on substrate, is i.e. acquisition anti-blue light optical material;
It is highly preferred that the step IV uses dip-coating method, concrete operations are as follows: pretreated optical substrate being immersed in anti-
It in blue light coating solution, impregnates 3-5 minutes, then by the slow lift-off coating solution of optical substrate, is moved in baking oven at room temperature, be arranged
Temperature is toasted 45-90 minutes at 35-65 DEG C, forms first layer anti-blue light coating;Then optical substrate is immersed in anti-indigo plant
In light coating liquid, impregnates 3-5 minutes, then by the slow lift-off coating solution of optical substrate, be moved in baking oven at room temperature, setting temperature
Degree toasts 45-90 minutes at 35-65 DEG C, forms second layer anti-blue light coating, obtains anti-blue light optical material.
8. the difunctional coated optical material of anti-blue light/discoloration as claimed in claims 6 or 7, which is characterized in that the polysulfide generation
Carbamate monomer is 2,2 '-dimercaptoethylsulfides, 2,2 '-dimercapto ethylenebis dithiocarbamate ethane, 2,3- dimercapto ethylenebis dithiocarbamate
Propanethiol or 1, at least one of 2,3- tri-thiol ethylenebis dithiocarbamate propane;
Preferably, the isocyanate-based curing agent is diisocyanate curing agent, 4,4 '-two isocyanide of diphenyl methane-
Acid esters curing agent, 1,6- di-isocyanate curing agent, m-xylylene diisocyanate curing agent, methyl cyclohexyl two are different
At least one of cyanate curing agent and isophorone diisocyanate curing agent;
Preferably, the diluent be methylene chloride, butyl acetate, methyl acetate, ethyl alcohol, butanol, acetone, toluene, dimethylbenzene,
At least one of ether and polytetrahydrofuran ether glycol.
9. such as the difunctional coated optical material of anti-blue light/discoloration of any of claims 1-8, which is characterized in that institute
State optical substrate be optical glass, optical plastic or optical crystal, the anti-blue light coating with a thickness of 10~100 μm.
10. the preparation method of the difunctional coated optical material of anti-blue light/discoloration of any of claims 1-9, special
Sign is that this method can choose one of following two scheme:
Scheme one: being first coated with the anti-blue light coating solution, after being fully cured, is coated with photochromic coating;
Scheme two: label optical substrate tow sides, front is first contacts ray surface, and reverse side contacts ray surface after being, front applies
Photochromic coating is covered, reverse side coats anti-blue light coating.
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Cited By (3)
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CN114031725A (en) * | 2021-10-25 | 2022-02-11 | 江苏视科新材料股份有限公司 | Preparation method of resin lens for correcting color vision |
CN116769345A (en) * | 2023-06-19 | 2023-09-19 | 江苏视科新材料股份有限公司 | Blue light discoloration prevention coating liquid, optical filter and preparation method of optical filter |
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