CN114509914A - Photo-curing composition, optical film, preparation method of optical film and optical product - Google Patents

Photo-curing composition, optical film, preparation method of optical film and optical product Download PDF

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Publication number
CN114509914A
CN114509914A CN202011280793.9A CN202011280793A CN114509914A CN 114509914 A CN114509914 A CN 114509914A CN 202011280793 A CN202011280793 A CN 202011280793A CN 114509914 A CN114509914 A CN 114509914A
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China
Prior art keywords
resin
substituted
oxetane
optical film
unsubstituted
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Inventor
钱晓春
张学龙
于培培
张宴成
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority to CN202011280793.9A priority Critical patent/CN114509914A/en
Priority to PCT/CN2021/130908 priority patent/WO2022100753A1/en
Publication of CN114509914A publication Critical patent/CN114509914A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/02—Simple or compound lenses with non-spherical faces
    • G02B3/08—Simple or compound lenses with non-spherical faces with discontinuous faces, e.g. Fresnel lens
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings

Abstract

The invention provides a photocuring composition, an optical film, a preparation method of the optical film and an optical product. The photo-curing composition comprises a monomer, a cationic photoinitiator, a photosensitive resin and an antioxidant, wherein the monomer is an oxetane monomer compound, and the structural formula of the oxetane monomer compound is shown in the specification
Figure DDA0002780680200000011
Wherein R is1Is selected from C1～C5Any one of substituted or unsubstituted alkyl of (1), R2Is selected from C1～C40Substituted or unsubstituted straight-chain alkyl, C3～C40And at least one carbon or hydrogen in the straight-chain alkyl group, the branched-chain alkyl group is substituted or unsubstituted by C6～C30Substituted or unsubstituted aryl, C3～C10Is substituted with one of the substituted or unsubstituted heteroaryl groups. The light-cured composition containing the oxetane compound is applied to the manufacturing of the optical film, and has the advantages of easy demoulding, high good yield and the like.

Description

Photo-curing composition, optical film, preparation method of optical film and optical product
Technical Field
The invention relates to the technical field of photocuring materials, and particularly relates to a photocuring composition, an optical film, a preparation method of the optical film and an optical product.
Background
With the rapid development of display technologies such as liquid crystal display devices, optical films used for these devices include prism sheets used for backlights of liquid crystal display devices and the like, lenticular lens sheets used for stereograms, projection screens and the like, fresnel lens sheets used for condenser lenses of overhead projectors and the like, diffraction gratings used for color filters and the like, and shaped illumination films used for game machines, toys, home appliances and the like. Such an optical film is also called a shaped film, and generally includes a base material and a shaped layer laminated on the base material. Desired optical properties can be imparted by transferring the fine shape to the shaping layer using a mold or the like.
The conventional optical film process is mostly manufactured by optical grinding or precision cutting with a diamond tool, and has the disadvantages of high production difficulty, low yield, time and labor consumption, high cost and easy damage. Therefore, optical manufacturers have developed processing techniques for molding optics to produce resins to meet the enormous market demand. For example, in the current lens manufacturing, the baking time of the thermosetting resin lens (for example, trade name CR-39) produced by the industry at present is as long as 20 hours, while the curing speed of the photo-curing resin lens is much faster in the production, and the curing can be completed only in a few seconds to ten minutes, thereby greatly improving the production efficiency of the resin lens. The photocuring is completed in a very short time (from a few seconds to ten minutes), the photocuring polymerization is an exothermic reaction, reaction heat is accumulated in the lens, the thermal expansion degree of the lens for enhancing the optical effect of the zoom (myopia lens) and the zoom (presbyopic lens) is different due to different thicknesses, and the larger the thickness is (the edge part of the myopia lens or the central part of the presbyopic lens), the larger the expansion degree is; whereas the expansion is much lower for thinner parts of the lens. If the difference in expansion is too great, the more expansive part will hold the mold open before curing is complete, causing the thinner part of the lens to prematurely break away from the mold, resulting in deformation or even chipping.
Disclosure of Invention
The invention mainly aims to provide a photocuring composition, an optical film, a preparation method thereof and an optical product, and aims to solve the problems of low yield, easiness in changing and falling of the optical film in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photocurable composition comprising a monomer, a cationic photoinitiator, a photosensitive resin, and an antioxidant, the monomer being an oxetane monomer compound having the structural formula
Figure BDA0002780680190000011
Wherein R is1Is selected from C1～C5Any one of substituted or unsubstituted alkyl of (1), R2Is selected from C1～C40Substituted or unsubstituted straight-chain alkyl, C3～C40And carbon or hydrogen in the straight chain alkyl, branched alkyl may be substituted by one or more hydroxyl groups, ether linkages, ester groups, -S (O)2-、C6～C30Substituted or unsubstituted aryl, C3～C10Substituted or unsubstituted heteroaryl or
Figure BDA0002780680190000021
Substituted and at least one carbon or hydrogen of straight-chain alkyl, branched-chain alkyl is replaced by C6～C30Substituted or unsubstituted aryl, C3～C10Is substituted with one of the substituted or unsubstituted heteroaryl groups.
Further, the above R1Is ethyl, R2Is selected from C1～C10Substituted or unsubstituted straight-chain alkyl, C3～C10Any one of substituted or unsubstituted branched alkyl groups.
Further, at least one carbon or hydrogen in the above-mentioned straight-chain alkyl group, branched-chain alkyl group is replaced by C6～C25Is gotSubstituted or unsubstituted aryl, C3～C5Preferably at least one carbon or hydrogen of the linear alkyl group, the branched alkyl group is substituted by one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted 9, 9-diphenylfluorenyl group, and further preferably at least one carbon or hydrogen of the branched alkyl group is substituted by one of a phenyl group, a tolyl group, a biphenyl group, and a 9, 9-diphenylfluorenyl group.
Further, the oxetane monomer compound is selected from
Figure BDA0002780680190000022
Figure BDA0002780680190000031
Figure BDA0002780680190000032
Preferably, the viscosity of the oxetane monomer compound is 8 to 3000cps, and the refractive index of the oxetane monomer compound is not less than 1.499.
Further, the antioxidant is a phenolic antioxidant, and preferably the phenolic antioxidant is one or more selected from the group consisting of butylated hydroxyanisole, dibutylhydroxytoluene, propyl gallate, t-butylhydroquinone, tea polyphenols, and 2, 4-dimethyl-6-styrylphenol.
Further, the photo-curing composition comprises 1 to 99 parts by weight of a monomer, 0.1 to 10 parts by weight of a cationic photoinitiator, 1 to 99 parts by weight of a photosensitive resin, and 1 to 30 parts by weight of an antioxidant.
Furthermore, the light-cured composition also comprises 0.1-100 parts by weight of an auxiliary agent, and preferably the auxiliary agent is selected from any one or more of a stabilizer, a release agent, a wetting agent, a dispersing agent, a slipping agent, a rheology modifier, a defoaming agent and a reinforcing agent.
Further, the cationic photoinitiator is selected from any one or more of iodonium salts and sulfonium salts.
Further, the photosensitive resin is selected from one or more of an oxetane resin, an epoxy resin, a vinyl ether resin and an amino resin compound, and preferably the oxetane resin is selected from a bisphenol A type oxetane resin, a bisphenol F type oxetane resin, a biphenyl type oxetane resin, a phenol novolak type oxetane resin, a cresol novolak type oxetane resin, a bisphenol A novolak type oxetane resin, an aliphatic polyoxyoxetane compound, a cyclic aliphatic oxetane resin, a rosin resin-modified oxetane resin, an oil-free alkyd resin-modified oxetane resin, an oleyl acid resin-modified oxetane resin, a phenolic resin-modified oxetane resin, an amino resin-modified oxetane resin, an acrylic resin-modified oxetane resin, a cellulose nitrate-modified oxetane resin, a cellulose-modified oxetane resin, Any one or more of silicone resin modified oxetane resins; preferably, the epoxy resin is selected from any one or more of bisphenol a type epoxy resins, bisphenol F type epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy resins, and epoxy compounds having a siloxane bonding site, and the epoxy equivalent of the epoxy resin is more than 200.
According to another aspect of the present invention, there is provided an optical film prepared using the aforementioned photocurable composition.
According to still another aspect of the present invention, there is provided a method of manufacturing the aforementioned optical film, the method including: step S1, mixing the monomer and the cationic photoinitiator in the photocurable composition under ultraviolet irradiation to form a first mixed solution; step S2, mixing the first mixed solution, the photosensitive resin and the antioxidant at the temperature of 0-20 ℃ to form a second mixed solution; step S3, defoaming the second mixed solution to obtain a defoamed mixed solution; and step S4, placing the mixed solution after defoaming into a forming die for forming at the temperature of 0-25 ℃ to obtain the optical film.
According to still another aspect of the present invention, there is provided an optical product including the optical film described above.
Further, the optical product is prism sheet, convex lens sheet, Fresnel lens sheet, diffraction grating.
By applying the technical scheme of the invention, as the oxetane compound has the advantages of low viscosity, small curing shrinkage and the like, the oxetane monomer is added into the photocuring composition, so that the viscosity and the reaction time of the photocuring composition can be obviously reduced, and the control on the flexibility of the polymer can be improved. The inventor of the invention surprisingly discovers that the defects that the stress of the light curing technology cannot be completely released, the thickness of the lens is uneven and the yield of the optical film is low are overcome by adopting the light-curing separation technology and utilizing the delayed curing characteristic of oxetane through careful research. Therefore, even if the oxetane compound having an aryl or heteroaryl structure is used alone, there is no fear of problems such as early mold release, low yield, and deformation due to failure to release the rapid curing stress of the optical element, and the requirements for the production environment (heat curing site) and the production technology (light source equipment, heat curing equipment) are reduced, and the production cost of the photocurable resin lens is reduced. Particularly, the oxetane compound of the application contains aryl or heteroaryl rigid groups, has higher refractive index, can greatly reduce the thickness of lenses in optical products when the optical film containing the oxetane compound is used for manufacturing the optical products, obtains light optical products, and overcomes the problems of high production energy consumption, bad production environment and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the prior art has the problems of low yield, easy variability and falling off of the optical film, and in order to solve the problems, the invention provides a photocuring composition, an optical film, a preparation method thereof and an optical product.
In one exemplary embodiment of the present application, a photocurable composition is provided, which includes a monomer, a cationic photoinitiator, a photosensitive resin, and an antioxidant, the monomer being an oxetane monomer compound having the structural formula
Figure BDA0002780680190000051
Wherein R is1Is selected from C1～C5Any one of substituted or unsubstituted alkyl, R2Is selected from C1～C40Substituted or unsubstituted straight-chain alkyl, C3～C40And carbon or hydrogen in the straight chain alkyl, branched alkyl may be substituted by one or more hydroxyl groups, ether linkages, ester groups, -S (O)2-、C6～C30Substituted or unsubstituted aryl, C3～C10Substituted or unsubstituted heteroaryl or
Figure BDA0002780680190000052
Substituted and at least one carbon or hydrogen of straight-chain alkyl, branched-chain alkyl is replaced by C6～C30Substituted or unsubstituted aryl, C3～C10Is substituted with one of the substituted or unsubstituted heteroaryl groups.
Because the oxetane compound has the advantages of low viscosity, small curing shrinkage and the like, the oxetane monomer is added into the photocuring composition, so that the viscosity and the reaction time of the photocuring composition can be obviously reduced, and the control on the flexibility of the polymer can be improved. The inventor of the invention surprisingly discovers that the defects that the stress of the light curing technology cannot be completely released, the thickness of the lens is uneven and the yield of the optical film is low are overcome by adopting the light-curing separation technology and utilizing the delayed curing characteristic of oxetane through careful research. Therefore, even if the oxetane compound having an aryl or heteroaryl structure is used alone, there is no fear of problems such as early mold release, low yield, and deformation due to failure to release the rapid curing stress of the optical element, and the requirements for the production environment (heat curing site) and the production technology (light source equipment, heat curing equipment) are reduced, and the production cost of the photocurable resin lens is reduced. Particularly, the oxetane compound of the application contains aryl or heteroaryl rigid groups, has higher refractive index, can greatly reduce the thickness of lenses in optical products when the optical film containing the oxetane compound is used for manufacturing the optical products, obtains light optical products, and overcomes the problems of high production energy consumption, bad production environment and the like.
For increasing the oxetane compound, the above-mentioned R is preferred1Is ethyl, R2Is selected from C1～C10Substituted or unsubstituted straight-chain alkyl, C3～C10Any one of substituted or unsubstituted branched alkyl groups.
In order to further increase the refractive index of the oxetane compound and thereby make thinner lenses, it is preferable that at least one carbon or hydrogen of the above-mentioned straight-chain alkyl group, branched-chain alkyl group is substituted with C6～C25Substituted or unsubstituted aryl, C3～C5Preferably at least one carbon or hydrogen of the linear alkyl group or branched alkyl group is substituted by one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted 9, 9-diphenylfluorenyl group, and further preferably at least one carbon or hydrogen of the branched alkyl group is substituted by one of a phenyl group, a tolyl group, a biphenyl group, a 9, 9-diphenylfluorenyl group.
In one embodiment of the present application, the oxetane monomer compound is selected from
Figure BDA0002780680190000061
Figure BDA0002780680190000071
Preferably oxa, in the presence of oxygenThe viscosity of the cyclobutane monomer compound is 8 to 3000cps, and the refractive index of the oxetane monomer compound is preferably not less than 1.499.
The oxetane monomer compound can fully exert the improvement effect on the properties such as the flexibility of the polymer, and the like, thereby improving the yield of the optical film. Controlling the viscosity of the oxetane monomer compound within the above range is more advantageous in controlling the viscosity of the photocurable composition, thereby facilitating the fabrication of an optical film. The control of the refractive index of the oxetane monomer compound is advantageous for obtaining an optical film which meets the optical performance requirements.
In order to improve the oxidation resistance of the photocurable composition and to obtain an optical film having excellent oxidation resistance, the antioxidant is preferably a phenolic antioxidant, and the phenolic antioxidant is preferably one or more selected from the group consisting of butylated hydroxyanisole, dibutylhydroxytoluene, propyl gallate, tert-butylhydroquinone, tea polyphenol, and 2, 4-dimethyl-6-styrylphenol.
In one embodiment of the present application, the photocurable composition comprises 1 to 99 parts by weight of a monomer, 0.1 to 10 parts by weight of a cationic photoinitiator, 1 to 99 parts by weight of a photosensitive resin, and 1 to 30 parts by weight of an antioxidant.
Controlling the content of each component in the photo-curing composition within the above range is beneficial to improving the synergistic effect among the components, thereby obtaining the photo-curing composition with better performance.
In order to further obtain optical films with various performances, the photocuring composition preferably further comprises 0.1-100 parts by weight of an auxiliary agent, and the auxiliary agent is preferably selected from one or more of a stabilizer, a release agent, a wetting agent, a dispersing agent, a slipping agent, a rheology modifier, a defoaming agent and a reinforcing agent.
The cationic photoinitiator is an important component of the cationic photocurable coating, can be photolyzed to generate active groups after being irradiated with light, can maintain the activity for a long time after being mixed with the monomer, and is preferably selected from one or more of iodonium salts and sulfonium salts in order to ensure that the photolytic agent can maintain the activity for a long time after being photolyzed. By way of example, the cationic moiety of the iodonium salt and sulfonium salt photoinitiators may have the following structures:
Figure BDA0002780680190000072
Figure BDA0002780680190000081
Figure BDA0002780680190000091
examples of the anionic moiety of the iodonium salt and sulfonium salt photoinitiators include: cl-、Br-、PF6 -、SbF6 -、AsF6 -、BF4 -、C4F9SO3 -、B(C6H5)4 -、C8F17SO3 -、CF3SO3 -、Al[OC(CF3)3]4 -、(CF3CF2)2PF4 -、(CF3CF2)3PF3 -、[(CF3)2CF2]2PF4 -、[(CF3)2CF2]3PF3 -、[(CF3)2CFCF2]2PF4 -、(CF3)2CFCF2]3PF3 -。
Commercially available cationic photoinitiators of the same type of structure may also be used for component (C) of the present invention, examples include (but are not limited to): PAG20001, PAG20001s, PAG20002s, PAG30201, PAG30101, etc., manufactured by Tronly, and Irgacure250, manufactured by BASF, etc.
The resin-based composite material has advantages such as light weight, high strength, designable mechanical properties, and the like, and in order to exhibit the advantages, the photosensitive resin is preferably selected from one or more of oxetane resins, epoxy resins, vinyl ether resins, and amino resin-based compounds, and the oxetane resin is preferably selected from bisphenol A-type oxetane resins, bisphenol F-type oxetane resins, biphenyl-type oxetane resins, phenol novolac-type oxetane resins, cresol novolac-type oxetane resins, bisphenol A novolac-type oxetane resins, aliphatic polyoxy-oxetane compounds, cyclic aliphatic oxetane resins, rosin resin-modified oxetane resins, oil-free alkyd resin-modified oxetane resins, oleyl acid resin-modified oxetane resins, phenolic resin-modified oxetane resins, epoxy resin-based resins, epoxy resin-modified oxetane resins, epoxy resin, Any one or more of amino resin modified oxetane resin, acrylic resin modified oxetane resin, cellulose nitrate modified oxetane resin and silicone resin modified oxetane resin; preferably, the epoxy resin is selected from any one or more of bisphenol a type epoxy resins, bisphenol F type epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy resins, and epoxy compounds having a siloxane bonding site, and the epoxy equivalent of the epoxy resin is more than 200.
In another exemplary embodiment of the present application, there is provided an optical film prepared using the aforementioned photocurable composition.
The oxetane compound of the photocuring composition has the advantages of low viscosity, small curing shrinkage and the like, and the oxetane monomer is added into the photocuring composition, so that the viscosity and the reaction time of the photocuring composition can be remarkably reduced, and the control on the flexibility of a polymer can be improved. The inventor of the invention surprisingly discovers that the defects that the stress of the light curing technology cannot be completely released, the thickness of the lens is uneven and the yield of the optical film is low are overcome by adopting the light-curing separation technology and utilizing the delayed curing characteristic of oxetane through careful research. Therefore, even if the oxetane compound having an aryl or heteroaryl structure is used alone, the problems of early demolding, low yield, deformation and the like caused by the fact that the rapid curing stress of the optical element cannot be released are not worried, so that the requirements on the production environment (a thermosetting place) and the production technology (light source equipment and thermosetting equipment) are reduced, and the production cost of the photo-curing resin lens is reduced.
The optical film with excellent optical performance is obtained by applying the light-cured composition containing the oxetane compound to the preparation of the optical film.
In still another exemplary embodiment of the present application, there is provided a method of manufacturing the aforementioned optical film, the method including: step S1, mixing the monomer and the cationic photoinitiator in the photocurable composition under ultraviolet irradiation to form a first mixed solution; step S2, mixing the first mixed solution, the photosensitive resin and the antioxidant at the temperature of 0-20 ℃ to form a second mixed solution; step S3, defoaming the second mixed solution to obtain a defoamed mixed solution; and step S4, placing the mixed solution after defoaming into a forming die for forming at the temperature of 0-25 ℃ to obtain the optical film.
The monomer and the photosensitive resin are polymerized by the action of the cationic photoinitiator to obtain a second mixed solution. The second mixed solution is defoamed and then is formed, so that an optical film with better compactness can be obtained, an optical product with better uniformity can be obtained, and excellent optical performance of the optical product can be exerted. In order to improve the forming efficiency, the temperature of the forming mold is set to be 25-100 ℃ after the mixed liquid after defoaming is put into the forming mold, and the temperature is kept for 1-5 min to obtain the formed optical film. Of course, in order to obtain a more refined optical film, it is preferable to obtain a final optical film by releasing the molded optical film from a mold, edging, washing, and drying.
In yet another exemplary embodiment of the present application, there is provided an optical product including an optical film that is the above-described optical film.
When the optical film of the present application is applied to the optical product, the excellent performance of the optical film of the present application can be further exerted, and the optical product with excellent optical performance can be obtained.
In an embodiment of the present application, the optical product is a prism sheet, a lenticular lens sheet, a fresnel lens sheet, or a diffraction grating.
The optical film of the present invention can be applied to the above-mentioned optical products to more fully exhibit the optical performance of the optical film of the present invention. The optical film of the present invention is used for, for example, a prism sheet used for a backlight of a liquid crystal display device or the like, a lenticular lens sheet used for a stereograph, a projection screen or the like, a fresnel lens sheet used for a condenser lens of a projector or the like, a diffraction grating used for a color filter, an optical sheet used for a game machine, a toy, a home appliance or the like, or an optical sheet used for a vehicle-mounted display.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Preparation of optical film
The preparation of an optical film is illustrated by example 1
Example 1
Mixing A-1 and B-1 at room temperature, and stirring under mercury lamp light source (5000 mJ/cm)2And 3min) to form a first mixed solution, adding the components C-1, D-1 and E-1 into the first mixed solution at 0 ℃, uniformly stirring to form a second mixed solution, and performing ultrasonic defoaming on the second mixed solution for 15min to obtain a defoamed mixed solution. And filling the defoamed mixed solution into a lens forming mold at 25 ℃, removing air in the mold, and laminating by using a rubber ring or an adhesive tape. Placing the mold into a constant temperature device, increasing the temperature of the mold to 10 deg.C, standing at constant temperature for 1minRaising the temperature to 25 ℃ for the second time, and keeping the temperature for 1 min; and raising the temperature to 35 ℃ for three times, keeping the temperature for 1min, taking out the die, demolding, edging, cleaning and drying to obtain the optical film, observing the quality of the product after the optical film is stripped, and performing performance test.
The following examples 2 to 10 were set by changing the kind of each component and the content of each component (the unit of the content of each component is parts by weight), as shown in table 1.
TABLE 1
Figure BDA0002780680190000111
Figure BDA0002780680190000121
Wherein, A-1:
Figure BDA0002780680190000122
a refractive index of 1.4999 and a viscosity of 8.1 cps;
A-2：
Figure BDA0002780680190000123
a refractive index of 1.5011 and a viscosity of 30.6 cps;
A-3：
Figure BDA0002780680190000124
a refractive index of 1.5069 and a viscosity of 240 cps;
A-4：
Figure BDA0002780680190000125
a refractive index of 1.5048 and a viscosity of 53.2 cps;
A-5：
Figure BDA0002780680190000131
a refractive index of 1.5325, a viscosity of 503 cps;
A-6：
Figure BDA0002780680190000132
a refractive index of 1.5109, a viscosity of 276 cps;
b-1 is tris (3-fluoro-4-methylphenyl) sulfonium hexafluorophosphate; b-2: 4,4' -ditolyl iodonium tetrakis (pentafluorophenyl) borate;
c-1: oxetane-modified bisphenol F epoxy resins; c-2, oxetane modified bisphenol S epoxy resin;
d-1: tea polyphenols; d-2: 2, 4-dimethyl-6-styrylphenol;
e-1 polyether-modified polydimethylsiloxane (mold release agent) containing acryloyl groups.
Example 11
Example 11 differs from example 1 in that the cationic photoinitiator is B-2, and an optical film is finally obtained.
Example 12
Example 12 differs from example 1 in that the photosensitive resin was C-2, and an optical film was finally obtained.
Example 13
Example 13 differs from example 1 in that the antioxidant was D-2, and an optical film was finally obtained.
Example 14
Example 14 differs from example 6 in that 99 parts by weight of A-5, 10 parts by weight of B-1, 99 parts by weight of C-1, 30 parts by weight of D-2 and 1 part by weight of E-1, and an optical film was finally obtained.
Example 15
Example 15 differs from example 6 in that 1 part by weight of A-5, 1 part by weight of B-1, 1 part by weight of C-1, 1 part by weight of D-2 and 0.1 part by weight of E-1, and an optical film was finally obtained.
Example 16
Example 16 differs from example 1 in that the components C-1, D-1 and E-1 were added to the first mixed solution at 20 ℃ and stirred uniformly to form a second mixed solution. At 0 deg.C, the mixed liquid after defoaming is filled into a lens forming mould, the air in the mould is removed, and a rubber ring or an adhesive tape is used for film combination. Placing the mold into a constant temperature device, raising the temperature of the mold to 10 ℃, standing at constant temperature for 1min, raising the temperature to 25 ℃ for the second time, and then keeping the temperature for 1 min; and raising the temperature to 35 ℃ for three times, keeping the temperature for 1min, taking out the die, demolding, edging, cleaning and drying to finally obtain the optical film, observing the quality of the product after the optical film is stripped, and performing performance test.
Comparative example 1
Comparative example 1 differs from example 1 in that the oxetane monomer compound is
Figure BDA0002780680190000141
And finally obtaining the optical film.
Comparative example 2
Comparative example 2 differs from example 1 in that 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate and B-1 were mixed uniformly and stirred under a mercury lamp light source (5000 mJ/cm)23min), partial curing occurs, and subsequent evaluation test operation cannot be performed.
Evaluation of Performance
(1) UV formability
The UV moldability of the optical films of examples 1 to 16, comparative example 1 and comparative example 2 was evaluated according to naked eyes, and the judgment criteria thereof were as follows: o: completely curing; x: and incomplete curing.
(2) Release force (releasability) of optical film
The optical films of examples 1 to 16, comparative example 1 and comparative example 2 were evaluated for releasability according to naked eyes on the following criteria: o: the mold can be completely demoulded; x: incomplete release or breakage of the optical film itself.
(3) Stress lines
The optical films of examples 1 to 16, comparative example 1 and comparative example 2 were visually evaluated for transparency after being placed on the diffusion film, respectively, on the following criteria: o: no stress lines; x: there are stress lines.
(4) Transparency of
The optical films of examples 1 to 16, comparative example 1 and comparative example 2 were respectively tested for transparency using an ultraviolet-visible glossmeter, and the criteria for judgment were as follows: o: the penetration rate is more than or equal to 92 percent; x: the penetration rate is less than 92 percent.
(5) Yellowing property
The yellowing of the optical films of examples 1 to 16, comparative example 1 and comparative example 2 were evaluated according to the naked eye, and the judgment criteria were as follows: o: no yellowing; o +: slightly yellow.
(6) Refractive index and Abbe number
The refractive indices and abbe numbers of the optical films of examples 1 to 16, comparative example 1 and comparative example 2 were respectively tested using a multi-wavelength refractive index machine (SCHMIDT HAENSCH).
(7) Impact resistance
The optical films of examples 1 to 16, comparative example 1 and comparative example 2 were tested for impact resistance with reference to the national standard GB/T5891-1986 ballistic eye protector test method: o: the optical film is not damaged; x: the optical film is cracked or cracked.
The results of the above tests are shown in Table 2.
TABLE 2
Figure BDA0002780680190000151
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
because the oxetane compound has the advantages of low viscosity, small curing shrinkage and the like, the oxetane monomer is added into the photocuring composition, so that the viscosity and the reaction time of the photocuring composition can be obviously reduced, and the control on the flexibility of the polymer can be improved. The inventor of the invention surprisingly discovers that the defects that the stress of the light curing technology cannot be completely released, the thickness of the lens is uneven and the yield of the optical film is low are overcome by adopting the light-curing separation technology and utilizing the delayed curing characteristic of oxetane through careful research. Therefore, even if the oxetane compound having an aryl or heteroaryl structure is used alone, there is no fear of problems such as early mold release, low yield, and deformation due to failure to release the rapid curing stress of the optical element, and the requirements for the production environment (heat curing site) and the production technology (light source equipment, heat curing equipment) are reduced, and the production cost of the photocurable resin lens is reduced. Particularly, the oxetane compound of the application contains aryl or heteroaryl rigid groups, has higher refractive index, can greatly reduce the thickness of lenses in optical products when the optical film containing the oxetane compound is used for manufacturing the optical products, obtains light optical products, and overcomes the problems of high production energy consumption, bad production environment and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. The photocuring composition comprises a monomer, a cationic photoinitiator, a photosensitive resin and an antioxidant, and is characterized in that the monomer is an oxetane monomer compound, and the structural formula of the oxetane monomer compound is shown in the specification
Figure FDA0002780680180000011
Wherein R is1Is selected from C1～C5Any one of substituted or unsubstituted alkyl of (1), R2Is selected from C1～C40Substituted or unsubstituted straight-chain alkyl, C3～C40And the carbon or hydrogen in the linear alkyl group, the branched alkyl group can be substituted by one or more hydroxyl, ether bond, ester group, -S (O)2-、C6～C30Substituted or unsubstituted aryl, C3～C10Substituted or unsubstituted heteroaryl or
Figure FDA0002780680180000012
And at least one carbon or hydrogen of said straight chain alkyl, said branched alkyl is substituted by C6～C30Substituted or unsubstituted aryl, C3～C10Is substituted with one of the substituted or unsubstituted heteroaryl groups.
2. The photocurable composition of claim 1 wherein R is1Is ethyl, said R2Is selected from C1～C10Substituted or unsubstituted said straight-chain alkyl, C3～C10Any of the substituted or unsubstituted branched alkyl groups.
3. Photocurable composition according to claim 1 or 2, characterized in that at least one carbon or hydrogen of said linear alkyl, branched alkyl is replaced by C6～C25Substituted or unsubstituted aryl, C3～C5Preferably at least one carbon or hydrogen of said linear alkyl group, said branched alkyl group is substituted by one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted 9, 9-diphenylfluorenyl group, further preferably at least one carbon or hydrogen of said branched alkyl group is substituted by one of a phenyl group, a tolyl group, a biphenyl group, a 9, 9-diphenylfluorenyl group.
4. The photocurable composition of any of claims 1-3 wherein the oxetane monomer compound is selected from the group consisting of
Figure FDA0002780680180000013
Figure FDA0002780680180000021
Figure FDA0002780680180000022
Preferably, the viscosity of the oxetane monomer compound is 8 to 3000cps, and the refractive index of the oxetane monomer compound is not less than 1.499.
5. The photocurable composition according to any one of claims 1 to 4, wherein the antioxidant is a phenolic antioxidant, preferably the phenolic antioxidant is selected from any one or more of butylated hydroxyanisole, dibutyl hydroxytoluene, propyl gallate, tert-butyl hydroquinone, tea polyphenols, 2, 4-dimethyl-6-styrene phenol.
6. The photocurable composition according to any one of claims 1-5, wherein the photocurable composition comprises 1-99 parts by weight of the monomer, 0.1-10 parts by weight of the cationic photoinitiator, 1-99 parts by weight of the photosensitive resin, and 1-30 parts by weight of the antioxidant.
7. The photo-curing composition as claimed in any one of claims 1 to 6, further comprising 0.1 to 100 parts by weight of an auxiliary agent, preferably the auxiliary agent is selected from any one or more of a stabilizer, a release agent, a wetting agent, a dispersant, a slip agent, a rheology modifier, a defoaming agent and a reinforcing agent.
8. The photocurable composition of claim 1 wherein the cationic photoinitiator is selected from any one or more of iodonium salts or sulfonium salts.
9. The photocurable composition according to claim 1, wherein the photosensitive resin is selected from one or more of oxetane resin, epoxy resin, vinyl ether resin and amino resin compound, preferably the oxetane resin is selected from bisphenol A type oxetane resin, bisphenol F type oxetane resin, biphenyl type oxetane resin, phenol novolac type oxetane resin, cresol novolac type oxetane resin, bisphenol A novolac type oxetane resin, aliphatic polyoxybutylene compound, aliphatic cyclo-oxetane resin, rosin resin modified oxetane resin, oil-free alkyd resin modified oxetane resin, oleyl acid resin modified oxetane resin, phenolic resin modified oxetane resin, amino resin modified oxetane resin, epoxy resin, amino resin modified oxetane resin, epoxy resin, Any one or more of acrylic resin modified oxetane resin, cellulose nitrate modified oxetane resin and silicone resin modified oxetane resin; preferably, the epoxy resin is selected from any one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, aliphatic polyglycidyl ether compound, cyclic aliphatic epoxy resin, and epoxy compound having a siloxane bonding site, and the epoxy equivalent of the epoxy resin is more than 200.
10. An optical film produced using the photocurable composition according to any one of claims 1 to 9.
11. A method for producing an optical film according to claim 10, comprising:
a step S1 of mixing the monomer and the cationic photoinitiator in the photocurable composition according to any one of claims 1-9 under ultraviolet irradiation to form a first mixed solution;
step S2, mixing the first mixed solution, the photosensitive resin and the antioxidant at the temperature of 0-20 ℃ to form a second mixed solution;
step S3, defoaming the second mixed solution to obtain a defoamed mixed solution; and
and step S4, at the temperature of 0-25 ℃, placing the defoamed mixed solution into a forming mold for forming to obtain the optical film.
12. An optical product comprising an optical film, wherein the optical film is the optical film of claim 10.
13. The optical product according to claim 12, wherein the optical product is a prism sheet, a lenticular sheet, a fresnel lens sheet, a diffraction grating.
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