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CN116854958B - A method for preparing a blue light-proof photochromic lens substrate - Google Patents

A method for preparing a blue light-proof photochromic lens substrate Download PDF

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Publication number
CN116854958B
CN116854958B CN202310694357.3A CN202310694357A CN116854958B CN 116854958 B CN116854958 B CN 116854958B CN 202310694357 A CN202310694357 A CN 202310694357A CN 116854958 B CN116854958 B CN 116854958B
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blue light
temperature
weight
photochromic
light
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CN116854958A (en
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毕志刚
王明华
蹇锡高
王锦艳
宗立率
纪立军
邹永存
唐创
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Jiangsu Shike New Material Co ltd
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Jiangsu Shike New Material Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00278—Lenticular sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings

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  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • Eyeglasses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种防蓝光光致变色镜片基片的制备方法，该方法包括将热固性或热塑性光学树脂单体25～100重量份、稀释剂0～0.8重量份、光致变色材料0.6～3重量份、固化剂0.5～3重量份、卟吩金属络合物0.1～1重量份和喹酞酮化合物0.2～0.8重量份制成镜片基材混料，然后浇筑在模具中，通过程序升温固化成型。该方法制备的镜片能实现对室内LED光源高能蓝光防护与户外光照变色后紫外线防护双功能。由卟吩金属络合物和喹酞酮化合物复配的蓝光吸收材料，在保持高透光率的前提下，对400‑435nm光谱区高能蓝光有特征吸收，且对紫外光有部分透过，不影响光致变色材料在强光下的的变色功能，耐候性佳。A method for preparing a blue light-proof photochromic lens substrate, the method comprising preparing a lens substrate mixture of 25 to 100 parts by weight of a thermosetting or thermoplastic optical resin monomer, 0 to 0.8 parts by weight of a diluent, 0.6 to 3 parts by weight of a photochromic material, 0.5 to 3 parts by weight of a curing agent, 0.1 to 1 parts by weight of a porphine metal complex and 0.2 to 0.8 parts by weight of a quinophthalone compound, and then pouring it into a mold, and curing and molding it by programmed temperature rise. The lens prepared by the method can achieve dual functions of protecting against high-energy blue light from indoor LED light sources and protecting against ultraviolet rays after discoloration of outdoor light. The blue light absorbing material compounded by the porphine metal complex and the quinophthalone compound has characteristic absorption of high-energy blue light in the 400-435nm spectral region while maintaining high light transmittance, and partially transmits ultraviolet light, does not affect the color-changing function of the photochromic material under strong light, and has good weather resistance.

Description

Preparation method of blue light prevention photochromic lens substrate
Technical Field
The invention relates to a preparation method of a blue light prevention photochromic resin lens substrate, in particular to a preparation method of a photochromic resin lens substrate capable of effectively absorbing high-energy blue light in a spectrum region of 400-435nm, and belongs to the technical field of resin lens manufacturing.
Background
The display manufacturing technology of the white light LED as a backlight system of a display device becomes a mainstream product technology of the existing electronic display technology, and such a display screen is widely applied to mobile communication terminal equipment, computer equipment, household and commercial display equipment, entertainment equipment and the like. Blue light hazard and "blue-rich" photo biosafety problems due to white LEDs are significant technical drawbacks of such display screens. The optical radiation hazard of the white light LED is mainly shown that short-wavelength high-energy blue light with a peak value of about 435nm can cause photochemical damage of retina and apoptosis of pigment epicutaneous cells. The short-wave blue light has higher energy and stronger tissue penetrating capability, has definite destructive action on the biological photosensitive group of mammals, and can cause retinopathy. Pathological studies prove that the high-energy blue light in the white light LED plays a certain acceleration role in the formation mechanism of the age-related macular degeneration. Because the macula retinae of children have weak blue light absorption capacity, the transmitted blue light radiation quantity is about twice that of adults under the same illumination intensity, and the blue light radiation is more harmful to the retinas of children. If the low-age population in the growth and development period is in a high-energy blue light environment for a long time, the light population induces blindness, and the heavy population causes lifelong vision to be low.
The ultraviolet region accounts for about 7% of the total solar radiation energy, and excessive ultraviolet radiation in outdoor activities can cause photochemical reactions of biological tissues, and especially damage to human skin, eyes, immune systems and the like. The human eyes are the most sensitive parts to ultraviolet rays, the ultraviolet rays are exposed for a long time and a plurality of times, acute conjunctivitis and retina diseases can be caused, and the ultraviolet rays are also an important cause of senile cataract.
Thus, functional protective lenses that protect vision, safeguarding eye health, have now become high profit products for the lens market. The development technology of the photochromic lens under the strong light environment of outdoor activities is mature and stable, various light background color and background color-free photochromic sunglasses are sold for years to obtain market approval, the high-energy blue-light protection glasses in the indoor dark light environment are also popular industries in the lens market, and on the basis, the requirements of high-energy blue-light protection of personnel in contact with electronic display equipment are combined, so that innovative glasses with the dual functions of outdoor photochromic and indoor high-energy blue-light protection are developed in recent years.
The human eyes are insensitive to visible matters and color discrimination of blue light in the range of 400-440nm, the wavelength of the light wave in the wave band is high in short energy, harmful blue light is greatly damaged to eyes, the high-energy blue light protective lens has low transmittance to the blue light, the damage to the eyes by the blue light in the range of 440-500nm is relatively small, the biological rhythm and optic nerve feedback action of the human body can be effectively regulated, the color judgment of the eyes on an observed object is kept accurate, and a certain transmittance to the blue light is kept.
The photochromic lens is also called as a photosensitive lens, and can be darkened rapidly to block strong light and absorb ultraviolet rays but not absorb visible light when being irradiated by ultraviolet rays in outdoor light when the indoor light and the outdoor light are switched according to a molecular reaction mechanism with reversible light color interconversion, and can fade rapidly to recover a colorless transparent state when being switched back to an indoor low-ultraviolet or ultraviolet-free environment so as to ensure the transmittance of the lens. Therefore, the photochromic lens can be used indoors and outdoors, and can effectively prevent the damage of sunlight, ultraviolet light and glare to eyes.
The main technical problem of combining the photochromic lens with the blue light protection function is that various organic blue light absorption protection materials with the largest use amount exist certain spectral absorption in an ultraviolet light region, particularly in a specific ultraviolet light spectral region capable of inducing the photochromic material to change color, the photochromic lens is mixed with the photochromic material to produce the blue light prevention photochromic lens, the adding amount of the photochromic material is increased by multiple levels, the manufacturing cost is greatly improved, the color changing and fading speed when the photochromic lens is used as the function is influenced, the color changing strength is low, the fading does not thoroughly exist, and poor use experience is brought to consumers.
Therefore, on the premise of ensuring effective absorption of high-energy blue light, the development of the application of the organic blue light absorbing material which is free from absorption in the ultraviolet region, low in industrial production and processing cost and high in weather resistance to blue light-proof photochromic lenses and blue light-proof membrane products is sought and has obvious commercial value.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a blue light-preventing photochromic lens substrate containing a compound blue light absorbing material and a photochromic material, and the lens substrate prepared by the method can realize dual functions of high-energy blue light protection of an indoor LED light source and ultraviolet protection after outdoor illumination discoloration. The blue light absorbing material compounded by the porphin metal complex and the quinophthalone compound has characteristic absorption to high-energy blue light in a spectrum region of 400-435nm on the premise of keeping high light transmittance, and has partial transmission to ultraviolet light, does not influence the color changing function of the photochromic material under strong light, and has good weather resistance.
In order to achieve the above purpose, the invention comprises the following technical scheme:
A preparation method of a blue light prevention photochromic lens substrate comprises the following steps:
I. Substrate formulation
Preparing base material ingredients according to the following components and proportions, namely, 25-100 parts by weight of thermosetting or thermoplastic optical resin monomer, 0-0.8 part by weight of diluent, 0.6-3 parts by weight of photochromic material, 0.5-3 parts by weight of curing agent, 0.1-1 part by weight of porphine metal complex and 0.2-0.8 part by weight of quinophthalone compound;
The porphin metal complex is selected from at least one of the following structures of A type, octaethyl porphin zinc, B type, octaethyl porphin nickel, C type, 5,10,15, 20-tetra (pentafluorophenyl) porphin zinc, D type tetraphenyl porphin zinc;
The quinophthalone compound has the following structural formula:
II, preparing a lens substrate mixture
A. The preparation of the acrylic ester base material comprises the following steps of accurately weighing all the base material ingredients except the curing agent, mixing, stirring until the base material ingredients are completely dissolved, adding the curing agent at the temperature of 20-30 ℃, and stirring for 1-2 hours to uniformly mix the base material ingredients to obtain a lens base material mixture;
b. The preparation of the polyurethane resin base material comprises the following steps of accurately weighing all the base material ingredients except the curing agent, mixing, stirring until the base material ingredients are completely dissolved, adding the curing agent, sealing and stirring at the temperature of 30-40 ℃, cooling ice water to 15-20 ℃, stirring in vacuum, stopping stirring until the temperature reaches the room temperature, and obtaining the lens base material mixture.
III, pouring and forming
After the mixing and defoaming of the lens base material, keeping the temperature of the material to be 15-30 ℃, filtering by a tetrafluoroethylene filter screen with the aperture smaller than 0.1 mu m under the condition of inert gas pressurization, injecting the filtered material into a lens mold through a feeding device, carrying out programmed heating, curing and molding in a curing furnace with computer temperature control, cooling to 70-80 ℃, and removing the mold to obtain the lens base material.
In the preparation method, preferably, the temperature programming operation in the step III is to perform temperature programming from room temperature to 95-100 ℃ within 18-22 hours, and then the temperature is kept for 1.5-2.0 hours, so as to finish the solidification molding.
In the preparation method, the base material ingredients are preferably prepared according to the following components and proportions, namely 50-100 parts by weight of thermosetting or thermoplastic optical resin material, 0-0.6 part by weight of diluent, 0.6-2.5 parts by weight of photochromic material, 0.5-3 parts by weight of curing agent, 0.1-1 part by weight of porphine metal complex and 0.2-0.8 part by weight of quinophthalone compound.
The preparation method as described above, preferably, the thermosetting or thermoplastic optical resin monomer is selected from one or more of m-xylylene diisocyanate, styrene, methacrylic acid, polyethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol a epoxy acrylate, methylstyrene, polyacrylate, ethoxylated bisphenol a diacrylate and butyl methacrylate.
The preparation method is characterized in that the curing agent is preferably selected from one or more of dibutyl tin dilaurate, diisopropyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexyl carbonate, 1' -azo (cyanocyclohexane), diisopropyl azodicarbonate, azodiisoheptonitrile, dimethyl azodiisobutyrate, diethyl azodiisobutyrate, cumene hydroperoxide and tert-butyl hydroperoxide.
The preparation method is characterized in that the photochromic material is preferably spiropyran and/or spirooxazine photochromic material.
The preparation method is characterized in that the photochromic material is N- (beta-hydroxyethyl) -3, 3-dimethyl-6-nitrospiroindoline benzopyran, 1, 3-trimethylindole-6-nitrobenzodihydropyran spiroalkane and/or 1, 3-trimethylindole-beta-naphthyl dihydrofuran.
The preparation method is characterized in that the diluent is preferably one or more of toluene, xylene, alkyl methacrylate, hydroxyethyl methacrylate, pentaerythritol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, n-butanol and trimethylolpropane.
The beneficial effects of the invention are as follows:
1. The invention replaces the prior art using benzophenone, benzotriazole or alkyl indole and other conventional organic micromolecular blue light absorbers with selective porphine complex and quinophthalone composite blue light absorbing material. The composite blue light absorbing material has certain transmission in the ultraviolet spectrum region, ensures the ultraviolet radiation intensity required by photochromism, avoids the color-changing interference of the blue light preventing material on the photochromism material, simultaneously has characteristic absorption on high-energy blue light in the spectrum region of 400-435nm on the premise of keeping high light transmittance, and realizes the dual functions of high-energy blue light protection of an indoor LED light source and ultraviolet protection after outdoor illumination color change.
2. Compared with the prior art, the composite blue light absorbing material has remarkable blue light prevention effect under the condition of less addition, the average cut-off rate of blue light with the wavelength of 400-435nm is more than 80%, the addition of the photochromic material is reduced by more than 50%, the production cost is reduced, and the influence on various physical properties of the lens is small.
3. The blue light-proof photochromic lens prepared by the invention has strong light stability and good weather resistance. Solves the problems of low color-changing strength and incomplete color fading existing in the existing blue-light-preventing photochromic resin lens production technology, can be widely applied to the fields of automobile windows, optical protective glass, LED lamp protective films, mobile phone protective screens, ophthalmic protective equipment and the like, and solves the problem that ultraviolet rays and LED light sources harm high-energy blue light to human eyes.
Drawings
FIG. 1 is a graph of spectral transmittance of lenses prepared in example 2.
Fig. 2 is a graph of spectral transmittance of the lenses prepared in comparative example 1.
Fig. 3 is a graph of spectral transmittance of the lenses prepared in comparative example 2.
Fig. 4 is a graph of the spectral transmittance contrast of lenses prepared in comparative examples 3 and 4.
Fig. 5 is a graph of spectral transmittance of lenses prepared in comparative example 5.
FIG. 6 is a graph of spectral transmittance of lenses prepared in comparative example 6.
FIG. 7 is a graph of spectral transmittance of lenses prepared in comparative example 7.
Fig. 8 is a graph of spectral transmittance of the lenses prepared in comparative example 8.
Fig. 9 is a graph of spectral transmittance of lenses prepared in comparative example 9.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were either commercially available from conventional sources or may be obtained by prior art methods unless specifically indicated. Unless otherwise indicated, assays or testing methods are routine in the art. The embodiments of the present invention are not limited by the following examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent substitutions and are included within the scope of the present invention.
The sources of some of the raw materials in the following examples are as follows:
Octaethylporphine zinc (type A) brand name SK408, available from Jiangsu-visual New Material Co., ltd
Octaethylporphine Nickel (type B) brand name SK316, available from Jiangsu-visual New Material Co., ltd
5,10,15, 20-Tetra (pentafluorophenyl) porphin zinc (C type) brand name SK318, new materials, inc. of Jiangsu visual family
Tetraphenylporphin Zinc (D type) brand name SK320, available from Jiangsu-visual New Material Co., ltd
N- (. Beta. -hydroxyethyl) -3, 3-dimethyl-6-nitrospiroindoline benzopyran, trade name of blue 274, new Material Co., ltd. Of Jiangsu-visual family
1, 3-Trimethylindole-6-nitrobenzodihydropyran spiroalkane, trade name of blue 275, new Material Co., ltd. Of Jiangsu visual family
1, 3-Trimethylindole-beta-naphthyldihydrofuran, new Material Co., ltd. In Jiangsu-visual family, trade name, blue 276
Quinophthalone compounds of formula I are prepared according to the method described in Chinese patent No. ZL 201710101651.3.
Example 1 blue-light-proof photochromic lens (I)
I. Preparation of A-type blue-light-discoloration-preventing composite resin
1500G of polyethylene glycol dimethacrylate is weighed, then 8g of A-porphine metal complex, 7g of quinophthalone (formula I), 20g of N- (beta-hydroxyethyl) -3, 3-dimethyl-6-nitrospiroindoline benzopyran photochromic material and 0.4g of xylene diluent are added, 500g of m-Xylylene Diisocyanate (XDI) and 15g of diisopropyl azodicarboxylate curing agent are added, and the mixture is stirred for 30 minutes at a temperature of 40 ℃ in a sealing way. Cooling ice water to 18 ℃, stirring in vacuum for 60 minutes, wherein the vacuum degree is-0.09 MPa, stopping stirring, and then cooling to room temperature to obtain the photochromic composite resin containing the A-type blue light absorbent.
II, preparing blue light prevention photochromic substrate
After ultrasonic defoaming of the photochromic composite resin containing the A-type blue light absorbent, maintaining the material temperature at 20 ℃, filtering by a polytetrafluoroethylene filter screen with the aperture of 0.1 mu m through nitrogen pressurization, injecting into a lens mold, and placing into a computer temperature-controlled curing furnace for programmed heating curing molding. The thermal curing temperature curve is as follows, the temperature is kept for 8 hours at 40 ℃, the temperature is evenly raised to 65 ℃ within 6 hours, the temperature is continuously raised to 100 ℃ and kept at the constant temperature for 2 hours, the temperature is reduced to 70 ℃ within 1 hour, and the curing is completed, so that the (polyurethane) resin blue-light-preventing photochromic substrate is obtained.
Example 2 blue-light-proof photochromic lens (II)
I. Preparation of B-type blue-light-discoloration-preventing composite resin
Weighing 25g of methyl styrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate and 25g of butyl methacrylate, then adding 0.3g of B-porphine metal complex, 0.25g of quinophthalone (formula I), 1.2g of 1, 3-trimethyl indole-6-nitrobenzodihydropyran spiral photochromic material, 0.8g of 1, 3-trimethyl indole-beta-naphthyl dihydrofuran photochromic material and 0.4g of xylene diluent, adding 2.0g of azo-diisoheptonitrile curing agent, vacuumizing for 30 minutes at room temperature, and continuously stirring and mixing uniformly in the process. And controlling the temperature at 35 ℃, stirring at 500r/min, standing and vacuumizing for 90 minutes. And obtaining the photochromic composite resin containing the B-type blue light absorbent.
II, preparing blue-light-proof photochromic lens substrate
After ultrasonic defoaming of a photochromic composite resin mixture containing a B-type blue light absorbent, maintaining the temperature at 20 ℃ (specific temperature), naturally filtering by a polytetrafluoroethylene filter screen filter with the temperature of 0.1 mu m, injecting into a lens mold for sealing, and heating to 100 ℃ from room temperature by a program in a curing oven with the temperature controlled by a computer for 20 hours, wherein the temperature programmed curve is that 35 ℃ is maintained for ① -4 hours, 60 ℃ is uniformly increased for ② -12 hours, 100 ℃ is uniformly increased for ③ -18 hours, 100 ℃ is maintained for ④ -20 hours, and the mold is opened after ⑤ is cooled to 70 ℃ to obtain the (acrylic ester) resin blue light prevention photochromic substrate.
Example 3 blue-light-proof photochromic lens (III)
I. Preparation of C-type blue-light-discoloration-preventing composite resin
Weighing 25g of methyl styrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate and 25g of butyl methacrylate, then adding 0.5g of C-porphine metal complex, 0.35g of quinophthalone (formula I), 1.0g of 1, 3-trimethyl indole-6-nitrobenzodihydropyran spiral photochromic material, 0.5g of 1, 3-trimethyl indole-beta-naphthyl dihydrofuran photochromic material and 0.4g of xylene diluent, adding 2.0g of azo-diisoheptonitrile curing agent, vacuumizing for 30 minutes at room temperature, and continuously stirring and mixing uniformly in the process. And controlling the temperature at 35 ℃, stirring at 500r/min, standing and vacuumizing for 90 minutes. And obtaining the photochromic composite resin containing the C-type blue light absorbent.
II, preparing blue-light-proof photochromic lens substrate
After ultrasonic defoaming of the photochromic composite resin containing the C-type blue light absorbent, the material temperature is kept at 20 ℃ (specific temperature), the material is naturally filtered by a polytetrafluoroethylene filter screen filter with the temperature of 0.1 mu m and then is injected into a lens mold for sealing, the temperature is programmed to be 100 ℃ from room temperature in a curing furnace with the temperature controlled by a computer for 20 hours, the programmed temperature curve is ① -4 hours and kept at 35 ℃, the temperature is ② -12 hours and is uniformly increased to 60 ℃, the temperature is ③ -18 hours and is uniformly increased to 100 ℃, the temperature is ④ -20 hours and kept at 100 ℃, the mold is opened after ⑤ is cooled to 70 ℃, and the (acrylic ester) resin blue light prevention photochromic substrate is obtained, washed and dried.
Example 4 blue-light-proof photochromic lens (IV)
I. preparation of D-type blue-light-discoloration-preventing composite resin
Weighing 25g of methylstyrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate and 25g of butyl methacrylate, then adding 1.0g of D-porphine metal complex, 0.6g of quinophthalone (formula I), 1.8g of quinophthalone (formula I), 0.6g of 1, 3-trimethyl indole-beta-naphthyl dihydrofuran photochromic material and 0.4g of xylene diluent, adding 2.2g of azo diisoheptonitrile curing agent, vacuumizing for 30 minutes at room temperature, and continuously stirring and mixing uniformly in the process. And controlling the temperature at 35 ℃, stirring at 500r/min, standing and vacuumizing for 90 minutes. Obtaining the photochromic composite resin containing the D-type blue light absorbent.
II, preparing blue-light-proof photochromic lens substrate
After ultrasonic defoaming of the photochromic composite resin containing the D-type blue light absorbent, the material temperature is kept at 20 ℃ (specific temperature), the material is naturally filtered by a polytetrafluoroethylene filter screen filter with the temperature of 0.1 mu m and then is injected into a lens mold for sealing, the temperature is programmed to be 100 ℃ from room temperature in a curing furnace with the temperature controlled by a computer for 20 hours, the programmed temperature curve is ① -4 hours and kept at 35 ℃, the temperature is ② -12 hours and is uniformly increased to 60 ℃, the temperature is ③ -18 hours and is uniformly increased to 100 ℃, the temperature is ④ -20 hours and kept at 100 ℃, the material is cooled to 70 ℃ by ⑤ and then is opened to obtain the (acrylic ester) resin blue light prevention photochromic substrate, and the blue light prevention photochromic substrate is cleaned and dried.
Example 5 blue-light-proof photochromic lens (five)
I. Preparation of A-type blue-light-discoloration-preventing composite resin
Weighing 25g of methylstyrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate and 25g of butyl methacrylate, then adding 0.8g of A-porphine metal complex, 0.8g of quinophthalone (formula I), 0.8g of 1, 3-trimethylindole-6-nitrobenzodihydropyran spiral photochromic material, 0.2g of 1, 3-trimethylindole-beta-naphthyl dihydrofuran photochromic material and 0.4g of xylene diluent, adding 2.2g of azo-diisoheptonitrile curing agent, vacuumizing for 30 minutes at room temperature, and continuously stirring and mixing uniformly in the process. And controlling the temperature at 35 ℃, stirring at 500r/min, standing and vacuumizing for 90 minutes. And obtaining the photochromic composite resin containing the A-type blue light absorbent.
II, preparing blue-light-proof photochromic lens substrate
After ultrasonic defoaming of photochromic composite resin containing A-type blue light absorbent, maintaining the temperature at 20 ℃, naturally filtering by a polytetrafluoroethylene filter screen filter with the thickness of 0.1 mu 0m, injecting into a lens mold for sealing, programming the temperature to 100 ℃ from room temperature in a curing furnace with the temperature controlled by a computer for 20 hours, wherein the programmed temperature curve is that the temperature is maintained at 35 ℃ for ① -4 hours, the temperature is increased to 60 ℃ at constant speed for ② -12 hours, the temperature is increased to 100 ℃ at constant speed for ⑦ -18 hours, the temperature is maintained at 100 ℃ for ④ -20 hours, the temperature is cooled to 70 ℃ for ④, and then the blue light prevention photochromic substrate of acrylate resin is obtained by mold opening, cleaning and drying.
Comparative examples 1 to 9
Comparative examples 1-9 each used the preparation conditions of the corresponding examples, except that the blue light absorber was replaced or that certain components were reduced, and the specific formulation conditions are detailed in Table 1. The total amount of the blue light absorber of each comparative example was the same as that of the corresponding example, and the color-changing material of each comparative example was the same as that of the corresponding example or was not added.
As a comparative commercially available conventional blue light absorber, 4- (1, 4-phenylene) bis (1- (4-butoxyphenyl) -1, 3-propanediol (China patent No. 108191624A) was used.
Table 1 comparative examples comparative tables prepared under different formulation conditions
Sample of Commercial blue light absorber Porphine metal complexes Quinophthalone Color-changing material Corresponding embodiment
Comparative example 1 0.3g / 0.25g √ Example 2
Comparative example 2 / / 0.55g √ Example 2
Comparative example 3 / 0.3g 0.25g / Example 2
Comparative example 4 / 0.85g / / Example 3
Comparative example 5 / 1.6g / √ Example 4
Comparative example 6 0.5g 0.8g / √ Example 5
Comparative example 7 15g / / √ Example 1
Comparative example 8 / 0.85 / √ Example 3
Comparative example 9 / / 1.3g / Example 5
Example 6 test of photochromic Property of blue-proof photochromic lens substrate
Test of photochromic response value
The detection step and method comprises the step of determining the ratio between the light transmittance tV (0) of the sample to be detected in a fading state and the light transmittance tV (1) of the sample to be detected in a color changing state after illumination time (15 min), namely, the photochromic response value = tV (0)/tV (1), so as to determine the photochromic response values of the sample to be detected at different temperatures. After the solar simulator radiation intensity was attenuated by 25%, the sample was irradiated with a medium illumination intensity, the test results are shown in fig. 1 to 9, and the test results are shown in table 2.
(II) photochromic Spectroscopy response time detection
The test procedure and method were carried out by placing the lens substrates prepared in examples 1-5 and comparative examples 1-9 into test boxes, respectively, turning on the light source of the solar simulator, recording the time required for the reaction of the lenses from colorless to colored, turning off the simulated light source after irradiation for 10 minutes, recording the time required for the lenses to recover from colored to colorless state, and the test results are shown in Table 2.
TABLE 2 detection of sample photochromic response values
The conclusion is that the optical material and the lens containing the compound blue light absorbing material have small influence on the color-changing performance, and have the advantages of short photochromic response time, high photochromic response value and the like.
Example 7 test of optical Property of blue-proof photochromic lens substrate
The resin lens substrates prepared in examples 1 to 5 and comparative examples 1 to 9 were each subjected to light transmittance (T/%) performance test using a Shanghai Yuan-Jiujia Co., ltd. UV-8000 ultraviolet-visible photometer. The detection method comprises directly coating the resin lenses prepared in examples 1-5 and comparative examples 1-8 on a prism of an ultraviolet-visible photometer to determine light transmittance, wherein the light transmittance is measured in a visible light region with a wavelength range of 380-780 nm and in an ultraviolet light region with a wavelength range of 280-380 nm, and different luminophores are adopted as light sources of the instrument. Representative wavelength transmittance is shown in table 3.
TABLE 3 optical transmittance detection of lens samples in units of T%
Results and discussion:
Comparing the above data, in comparative example 1, the porphine complex is changed into a common blue light absorber in the market, and the common blue light absorber absorbs ultraviolet light at the same time, so that the ultraviolet light absorption of the photochromic material is insufficient, the color change time is long, the color change effect is low, and the effect of rapid color change protection under strong light is not achieved;
Comparative example 2 contains no porphine complex only quinophthalone, and has ultraviolet protection lower than national standard (GB 10810.3-2006) requirements (less than or equal to 1 percent), and the ultraviolet protection item is not qualified;
Comparative example 3 does not discolor due to the absence of added color-changing material, and has transmission in the ultraviolet region around 335 nm;
Comparative example 4, with only porphin complex added, contains no quinophthalone and no color-changing material, has higher transmittance in the ultraviolet region around 335nm, and has higher transmittance of 435nm blue light than examples 1-5;
comparative example 5 without quinophthalone added, blue light transmittance at 435nm was higher than that of examples 1-5;
comparative example 6, with the addition of some commercial blue light absorber and no quinophthalone, resulted in low color-changing efficiency and higher blue light transmittance at 435 nm;
Comparative example 7 commercial blue light absorber substituted for the composite blue light absorber of the present invention resulted in lower color shifting efficiency and higher transmission at 435 nm;
Comparative example 8, with addition of only porphine complex, no quinophthalone, has higher blue light transmittance at 435 nm;
Comparative example 9 contains only quinophthalone, no porphine complex and no color-changing material, and has a high transmittance in the ultraviolet region around 335 nm.
The porphine metal complex (A-D) and quinophthalone adopted by the invention are combined, so that blue light with the wavelength of 400nm-435nm can be effectively absorbed, and the photochromic performance is not influenced.

Claims (6)

1.一种防蓝光光致变色镜片基片的制备方法，其特征在于，该方法包括如下步骤：1. A method for preparing a blue light blocking photochromic lens substrate, characterized in that the method comprises the following steps: I.基材配料I. Base material ingredients 按照以下成分和配比准备基材配料：热固性或热塑性光学树脂单体50～100重量份、稀释剂0～0.6重量份、光致变色材料0.6～2.5重量份、固化剂0.5～3重量份、卟吩金属络合物0.1～1重量份和喹酞酮化合物0.2～0.8重量份；Prepare the substrate ingredients according to the following ingredients and proportions: 50-100 parts by weight of thermosetting or thermoplastic optical resin monomer, 0-0.6 parts by weight of diluent, 0.6-2.5 parts by weight of photochromic material, 0.5-3 parts by weight of curing agent, 0.1-1 parts by weight of porphine metal complex and 0.2-0.8 parts by weight of quinophthalone compound; 该光致变色材料为螺吡喃类和/或螺噁嗪类光致变色材料；The photochromic material is a spiropyran and/or spirooxazine photochromic material; 该卟吩金属络合物选自以下结构的至少一种：A型，八乙基卟吩锌；B型，八乙基卟吩镍；C型，5,10，15,20-四(五氟苯基)卟吩锌；D型，四苯基卟吩锌；The porphine metal complex is selected from at least one of the following structures: Type A, octaethylporphine zinc; Type B, octaethylporphine nickel; Type C, 5,10,15,20-tetrakis(pentafluorophenyl)porphine zinc; Type D, tetraphenylporphine zinc; 该喹酞酮化合物的结构式如下：The structural formula of the quinophthalone compound is as follows: II.制备镜片基材混料II. Preparation of lens substrate mixture a.制备丙烯酸酯类基材采用以下操作：将上述各基材配料除固化剂外准确称量，混合后搅拌直至完全溶解，保持温度在20～30℃加入固化剂，搅拌1～2小时使其均匀混合，即制得镜片基材混料；a. Preparation of acrylic substrates by the following operation: accurately weigh the above-mentioned substrate ingredients except the curing agent, mix and stir until completely dissolved, add the curing agent while maintaining the temperature at 20 to 30 ° C, stir for 1 to 2 hours to make it uniformly mixed, and obtain a lens substrate mixture; b.制备聚氨酯树脂类基材采用以下操作：将上述各基材配料除固化剂外准确称量，混合后搅拌直至完全溶解，加入固化剂，在30-40℃温度下密封搅拌，冰水降温至15-20℃，真空搅拌，真空度为-0.09MPa，停止搅拌后至室温，即制得镜片基材混料；b. The following steps are used to prepare the polyurethane resin substrate: accurately weigh the above-mentioned substrate ingredients except the curing agent, mix and stir until completely dissolved, add the curing agent, seal and stir at a temperature of 30-40°C, cool to 15-20°C with ice water, stir in a vacuum, and the vacuum degree is -0.09MPa. After stopping stirring and returning to room temperature, the lens substrate mixture is obtained; III.浇注成型III. Casting 将镜片基材混料脱泡后，保持料温为15-30℃，惰性气体加压条件下通<0.1μm孔径四氟乙烯滤网过滤后，通过加料装置注入镜片模具中，在计算机控温的固化炉中程序升温固化成型，降温至70-80℃脱模具，即可制得镜片基片。After the lens substrate mixture is degassed, the material temperature is maintained at 15-30°C, filtered through a tetrafluoroethylene filter with a pore size of <0.1μm under inert gas pressure, injected into the lens mold through a feeding device, and cured in a computer-controlled temperature curing furnace by programmed temperature increase. The material is cooled to 70-80°C and then demolded to obtain the lens substrate. 2.如权利要求1所述的制备方法，其特征在于，所述步骤III程序升温操作是在18～22小时内从室温程序升温至95～100℃，然后保持该温度1.5～2.0小时，完成固化成型。2. The preparation method according to claim 1, characterized in that the programmed temperature operation in step III is to program the temperature from room temperature to 95-100°C within 18-22 hours, and then maintain the temperature for 1.5-2.0 hours to complete the curing molding. 3.如权利要求1或2所述的制备方法，其特征在于，所述热固性或热塑性光学树脂单体选自苯乙烯、甲基丙烯酸、季戊四醇四丙烯酸酯、乙氧化壬基酚丙烯酸酯、环氧丙烯酸酯、双酚A环氧丙烯酸酯、甲基苯乙烯、聚丙烯酸酯、乙氧化双酚A二丙烯酸酯和甲基丙烯酸丁酯中的一种或多种。3. The preparation method according to claim 1 or 2, characterized in that the thermosetting or thermoplastic optical resin monomer is selected from one or more of styrene, methacrylic acid, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol A epoxy acrylate, methyl styrene, polyacrylate, ethoxylated bisphenol A diacrylate and butyl methacrylate. 4.如权利要求1或2所述的制备方法，其特征在于，所述固化剂选自过氧化二碳酸二异丙酯、过氧化-2-乙基己基碳酸叔丁酯、1，1′-偶氮(氰基环己烷)、偶氮二甲酸二异丙酯、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮二异丁酸二乙酯、异丙苯过氧化氢、叔丁基过氧化氢中的一种或多种。4. The preparation method according to claim 1 or 2, wherein the curing agent is selected from the group consisting of diisopropyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexyl carbonate, 1,1′-azo (cyanocyclohexane), diisopropyl azodicarboxylate, azobisisoheptonitrile, dimethyl azobisisobutyrate, diethyl azobisisobutyrate, cumene hydroperoxide, and tert-butyl hydroperoxide. 5.如权利要求1或2所述的制备方法，其特征在于，所述光致变色材料为N-(β-羟乙基)-3,3-二甲基-6-硝基螺吲哚啉苯并吡喃、1，3,3-三甲基吲哚-6-硝基苯并二氢吡喃并螺烷和/或1，3，3-三甲基吲哚-β-萘基二氢呋喃。5. The preparation method according to claim 1 or 2, characterized in that the photochromic material is N-(β-hydroxyethyl)-3,3-dimethyl-6-nitrospiroindolinebenzopyran, 1,3,3-trimethylindole-6-nitrobenzodihydropyranospirane and/or 1,3,3-trimethylindole-β-naphthyldihydrofuran. 6.如权利要求1或2所述的制备方法，其特征在于，所述稀释剂为甲苯、二甲苯、甲基丙烯酸烷基酯、甲基丙烯酸羟乙酯、季戊四醇、乙二醇、丙二醇、丁二醇、己二醇、新戊二醇、正丁醇、三羟甲基丙烷中的一种或多种的混合物。6. The preparation method according to claim 1 or 2, characterized in that the diluent is a mixture of one or more of toluene, xylene, alkyl methacrylate, hydroxyethyl methacrylate, pentaerythritol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, n-butanol and trimethylolpropane.
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CN115785712A (en) * 2022-12-14 2023-03-14 江苏视科新材料股份有限公司 High-refractive-index blue-light-proof modified epoxy acrylate material and optical filter

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CN111187377A (en) * 2020-02-28 2020-05-22 江苏康耐特光学有限公司 Photochromic resin lens with refractive index of 1.50 and preparation method thereof
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