CN112300098B - Photopolymer composition, episulfide/epoxy writing monomer and grating - Google Patents
Photopolymer composition, episulfide/epoxy writing monomer and grating Download PDFInfo
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- CN112300098B CN112300098B CN202011184197.0A CN202011184197A CN112300098B CN 112300098 B CN112300098 B CN 112300098B CN 202011184197 A CN202011184197 A CN 202011184197A CN 112300098 B CN112300098 B CN 112300098B
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/34—Compounds containing oxirane rings with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms
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- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
The invention provides an episulfide/epoxy writing monomer which is shown as a formula (I); wherein X is an alkane group, thioether-containing group, ether bond-containing group, aromatic hydrocarbon group, cycloalkane hydrocarbon group or heterocyclic group formed in the absence of a + a' H; y and Y' are independently one or two or more of alkylene, arylene, S and O which are connected through a single bond; n and n' are each independently an integer of 0 to 2; z and Z' are each independently S or O; and X, Y,At least one of Y ', Z and Z' comprises S. Compared with the prior art, the invention effectively improves the refractive index of the monomer by introducing the sulfur element, and further improves the refractive index difference between the monomer and the film forming agent, thereby obtaining the photopolymer material with high refractive index modulation degree.
Description
Technical Field
The invention belongs to the technical field of optical materials, and particularly relates to a photopolymer composition, an episulfide/epoxy writing monomer and a grating.
Background
Holographic recording materials are materials that can record all information (including amplitude and phase) of object light waves in the form of interference fringes by using the principle of optical interference. In a typical processing mode, the element is formed by irradiation of visible light laser light to the photopolymer composition and the monomers in the photopolymer composition for holographic recording form (cured) polymers by polymerization, which can result in structural features in the element formed by the photopolymer composition that can form an interference pattern. Meanwhile, by modulating the refractive index, it is made possible to form a phase hologram having high diffraction efficiency. The photosensitive/photopolymer material has the characteristics of high sensitivity, high resolution, high signal-to-noise ratio, low cost, simple processing technology and the like, and is one of the most potential recording materials in the field of volume holographic devices.
Photosensitive/photopolymer systems as holographic recording materials typically comprise a dye, a photoinitiator, one or more monomers, a film former, and the like. After the polymer is irradiated by the recording light, the dye is excited by photons and then interacts with an initiator to generate free radicals or ions to initiate the polymerization of monomer molecules. The concentration of the monomer in the exposed area is reduced after polymerization, a monomer concentration gradient is formed between the monomer and the dark area, the monomer in the dark area is diffused to the bright area, the polymer is enriched in the bright area, and finally, the fixing is carried out through uniform exposure treatment, so that the residual monomer is completely polymerized, and finally, a phase hologram is formed in the medium. Therefore, theoretically, the larger the difference between the refractive indexes of the monomer and the film-forming agent is, the larger the refractive index modulation degree of the final photopolymer grating is.
DuPont (for example, U.S. Pat. Nos. 5013632, U.S. Pat. No. 4, 5098803, U.S. Pat. No. 4, 4950567, U.S. Pat. No. 8, 4959284, U.S. Pat. No. 4, 4987230, U.S. Pat. No. 4994347, U.S. Pat. No. 3, 5292620, U.S. Pat. No. 5402514), bordete, canon, fuji and Cork (Chinese patent publication Nos. CN107223121A, CN102667934B, and CN 102667936B) all proposed photosensitive/photopolymer holographic recording materials developed by themselves, but most of these products have the problems of insufficient refractive index modulation, insufficient angular selectivity, and are difficult to meet the requirements of wide FOV imaging systems in the market. Therefore, developing monomers with higher refractive index to improve the refractive index modulation degree and diffraction efficiency is one of the main research and development directions of the current photopolymer materials.
According to the Lorentz-Lorenz relation, the refractive index of the material is related to the molar volume of the material and the molar refractive index of the structure per se, and is shown as formula (1):
in the formula (1), n represents the refractive index of the material, [ R ]]Represents the molar refractive index, V, of the molecule 0 Representing the molar volume. It can be seen from equation (1) that higher refractive indices can be achieved if the material has a larger molar refractive index or a smaller molar volume. For example, the refractive index of the material can be effectively increased by introducing an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a heavy metal, or the like into the molecular structure. However, the molar dispersion of the aromatic ring is large, and excessive introduction can affect the optical performance of the polymer when the polymer is used as an optical material; meanwhile, the introduction of aromatic rings, bromine atoms and heavy metal elements can also reduce the solubility of the material; the stability of iodine is not good, and the introduction of iodine can reduce the light and heat stability of the material.
Disclosure of Invention
Accordingly, the present invention is directed to a photopolymer composition, an episulfide/epoxy writing monomer and a grating, wherein the episulfide/epoxy writing monomer has a high refractive index, a low viscosity and a high solubility, and is used in the photopolymer composition to increase the difference between the refractive index of the writing monomer and the refractive index of a film-forming agent, thereby obtaining a photopolymer composition having a high refractive index modulation degree.
The invention provides an episulfide/epoxy writing monomer, which is shown as a formula (I):
wherein X is an alkane group, thioether-containing group, ether bond-containing group, aromatic hydrocarbon group, cycloalkane hydrocarbon group or heterocyclic group formed in the absence of a + a' H;
when the atom connected with Y in X is S or O, a is 0 or 1;
when the atom connected with Y in X is C, a is an integer of 0-4;
when the atom connected with Y 'in X is S or O, a' is 0 or 1;
when the atom connected with Y 'in X is C, a' is an integer of 0-4;
and a' are not 0 at the same time;
y and Y' are independently one or two or more of alkylene, arylene, S and O which are connected by a single bond;
n and n' are each independently an integer of 0 to 2;
z and Z' are each independently S or O;
and at least one of X, Y, Y ', Z and Z' comprises S.
Preferably, X is CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' C6-C20 aromatic hydrocarbon groups lacking a + a ' H, C3-C20 naphthenic hydrocarbon groups lacking a + a ' H, or C2-C20 heterocyclic groups lacking a + a ' H; r, R' and R "are each independently H, alkyl, or aryl.
Preferably, Y and Y' are each independently one or two or more groups selected from C1-C4 alkylene, C6-C10 arylene, S and O, which are connected by a single bond.
Preferably, the episulfide/epoxy writing monomer is one or more of the formulas (II-1) to (II-11):
wherein m is 1 ～m 10 Each independently is an integer of 0 to 4; m is 2 '～m 7 '、m 9 ' and m 10 ' are each independently an integer of 0 to 4; n is 1 ～n 11 Each independently is an integer of 0 to 2; n is 2 '～n 7 '、n 9 '～n 11 ' are each independently an integer of 0 to 2;
a1 is an integer of 1 to 3;
R 1 ～R 4 each independently is H, C-C10 alkyl or C6-C20 aryl;
z and Z' are each independently S or O.
Preferably, the episulfide/epoxy writing monomer is one or more of compounds 1 to 7:
z and Z' are each independently S or O.
Preferably, the refractive index of the episulfide/epoxy writing monomer is greater than or equal to 1.60.
The present invention also provides a photopolymer composition comprising:
the polymeric monomer includes the episulfide/epoxy writing monomer described above.
Preferably, the polymerized monomer further comprises an acrylate monomer; the weight of the epoxy/episulfide writing monomer in the polymerized monomer is 20 to 70 percent of the weight of the polymerized monomer.
Preferably, the paint also comprises 10 to 50 weight parts of solvent and 0.1 to 5 weight parts of other additives;
the film forming agent is selected from one or more of vinyl acetate copolymer, cellulose ester, cellulose ether, polyvinyl alcohol, polyvinyl acetal, polyurethane, styrene-butadiene block copolymer and polyvinylpyrrolidone;
the photosensitive dye compound is selected from one or more of Irgacure 784, new methylene blue, thionine, basic Red 2, basic yellow, pinacyanol chloride, rhodamine 6G, betacyanin, ethyl violet, victoria blue R, azure blue, quinaldine Red, brilliant green, basic orange G, da Luo Gong, pyronin Y, rose Bengal, eosin Y, michler's ketone, 3,3' -carbonylbis (7-diethylaminocoumarin), iodonium pyrans, diiodofluorescein, anthocyanins, methylene blue, azure A, crystal violet and malachite green;
the coinitiator is one or more selected from ethylenediamine, N-phenylglycine, 2- (4-chlorphenyl) -4,5-diphenyl imidazole and 4-dimethyl-ethyl aminobenzoate.
The invention also provides a grating which is a resin film with a grating structure; the resin film is formed by curing the above-described polymerizable composition.
The invention provides an episulfide/epoxy writing monomer which is shown as a formula (I); wherein X is an alkane group, thioether-containing group, ether bond-containing group, aromatic hydrocarbon group, cycloalkane group or heterocyclic group which is deficient in a + a' H; when the atom connected with Y in X is S or O, a is 0 or 1; when the atom connected with Y in X is C, a is an integer of 0-4; when the atom connected with Y 'in X is S or O, a' is 0 or 1; when the atom connected with Y 'in X is C, a' is an integer of 0-4; and a' are not 0 at the same time; y and Y' are independently one or two or more of alkylene, arylene, S and O which are connected through a single bond; n and n' are each independently an integer of 0 to 2; z and Z' are each independently S or O; and at least one of X, Y, Y ', Z and Z' comprises S. Compared with the prior art, the invention effectively improves the refractive index of the monomer by introducing the sulfur element, and further improves the refractive index difference between the monomer and the film forming agent, thereby obtaining the photopolymer material with high refractive index modulation degree.
Drawings
FIG. 1 is a schematic structural diagram of a grating device according to the present invention;
FIG. 2 is a schematic diagram of an exposure light path during the preparation of a grating according to the present invention;
fig. 3 is a graph showing diffraction efficiency curves of the reflective hologram gratings obtained in example 1 of the present invention and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an episulfide/epoxy writing monomer, which is shown as a formula (I):
wherein X is an alkane group, thioether-containing group, ether bond-containing group, aromatic hydrocarbon group, cycloalkane hydrocarbon group or heterocyclic group formed in the absence of a + a' H, preferably CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' C6-C20 aromatic hydrocarbon group lacking a + a 'H, aromatic hydrocarbon group lacking a + a' HA C3-C20 cycloalkane group or a C2-C20 heterocyclic group lacking a + a' H, more preferably CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' An aromatic hydrocarbon group of C6 to C16 formed by the absence of a + a ' H, a cycloalkane group of C3 to C16 formed by the absence of a + a ' H, or a heterocyclic group of C2 to C16 formed by the absence of a + a ' H, and is preferably CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' An aromatic hydrocarbon group of C6 to C12 formed by the absence of a + a ' H, a cycloalkane group of C3 to C12 formed by the absence of a + a ' H, or a heterocyclic group of C2 to C12 formed by the absence of a + a ' H, and is preferably CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' C6-C12 aromatic hydrocarbon group lacking a + a ' H, C3-C8 cycloalkane group lacking a + a ' H, or C2-C8 heterocyclic group lacking a + a ' H, and is preferably CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' C6-C12 aromatic hydrocarbon group lacking a + a ' H, C3-C6 naphthenic hydrocarbon group lacking a + a ' H or C2-C6 heterocyclic group lacking a + a ' H, most preferably CR 4-a-a' 、SR' 2-a-a' 、OR” 2-a-a' A phenyl group that lacks a + a 'H, a biphenyl group that lacks a + a' H, a cyclopropyl group that lacks a + a 'H, a cyclobutyl group that lacks a + a' H, a cyclopentyl group that lacks a + a 'H, a cyclohexyl group that lacks a + a' H, a ternary heterocyclic group that lacks a + a 'H, a quaternary heterocyclic group that lacks a + a' H, a five-membered heterocyclic group that lacks a + a 'H, or a six-membered heterocyclic group that lacks a + a' H; the heteroatoms in the heterocyclic group are preferably S and/or O; the number of heteroatoms in the heterocyclic group is preferably 1 to 3, more preferably 1 to 2; r, R 'and R' are each independently H, alkyl or aryl, preferably H, C-C10 alkyl or C6-C20 aryl, more preferably H, C-C6 alkyl or C6-C16 aryl, still more preferably H, C-C4 alkyl or C6-C12 aryl, most preferably H, C-C2 alkyl or C6-C10 aryl; wherein the aryl group may be unsubstituted or substituted, and is not particularly limited.
When the atom connected with Y in X is S or O, a is 0 or 1;
when the atom connected with Y in X is C, a is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and most preferably 0 or 1;
when the atom connected with Y 'in X is S or O, a' is 0 or 1;
when the atom connected with Y 'in X is C, a' is an integer of 0-4, preferably an integer of 0-3, more preferably an integer of 0-2, and most preferably 0 or 1;
and a' are not 0 at the same time.
Y and Y' are independently one or two or more of alkylene, arylene, S and O which are connected through a single bond; the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3, and most preferably 1 to 2; the number of carbon atoms of the arylene group is preferably 6 to 20, more preferably 6 to 16, further preferably 6 to 12, further preferably 6 to 10, most preferably 6;
n and n' are each independently an integer of 0 to 2, more preferably 0 or 1;
z and Z' are each independently S or O;
and at least one of X, Y, Y ', Z and Z' comprises S, that is, the episulfide/epoxy writing monomer provided by the invention at least comprises one S atom, and the refractive index of the episulfide/epoxy writing monomer is preferably greater than or equal to 1.60, more preferably greater than or equal to 1.62, and still more preferably greater than or equal to 1.65 by introducing the sulfur atom.
Further preferably, in the present invention, the episulfide/epoxy writing monomer is one or more of the formulae (II-1) to (II-11):
wherein m is 1 ～m 10 Each independently is an integer from 0 to 4, preferably an integer from 0 to 3, and more preferably 0, 1 or 2; m is 2 '～m 7 '、m 9 ' and m 10 ' are each independently an integer of 0 to 4, preferably 0 to 3, and more preferably 0, 1 or 2; n is 1 ～n 11 Each independently is an integer of 0 to 2, preferably 0 or 1; n is 2 '～n 7 '、n 9 '～n 11 ' are each independently an integer of 0 to 2, preferably 0 or 1;
a 1 is an integer of 1 to 3, preferably 1 or 2;
R 1 ～R 4 each independently is H, C-C10 alkyl or C6-C20 aryl, preferably H, C-C6 alkyl or C6-C16 aryl, more preferably H, C-C4 alkyl or C6-C12 aryl, still more preferably H, C1-C3 alkyl or C6-C12 aryl, most preferably H, C-C2 alkyl or C6-C10 aryl; the aryl group may be substituted or unsubstituted, and is not particularly limited;
z and Z' are each independently S or O.
Further preferably, in the present invention, the episulfide/epoxy writing monomer is one or more of compounds 1 to 7:
z and Z' are each independently S or O.
The introduction of sulfur element effectively improves the refractive index of the monomer, further improves the refractive index difference between the monomer and the film forming agent, thereby obtaining the photopolymer material with high refractive index modulation degree.
The present invention also provides a method for preparing the episulfide/epoxy writing monomer, which can be prepared by a preparation method generally used in the field, preferably, when the episulfide/epoxy writing monomer is an epoxy monomer, the episulfide/epoxy writing monomer can be prepared by reacting epichlorohydrin with a phenol (oxyphenol or thiophenol), an alcohol or a thiol compound under an alkaline condition, and the formula is shown as follows:
the episulfide monomer can be further prepared by substitution reaction of epoxy monomer and potassium thiocyanate:
it should be noted that, in the present invention, episulfide monomer is mainly obtained by converting epoxy monomer, the conversion rate cannot reach 100%, and the actual conversion rate is about 50% -80%, therefore, episulfide/epoxy writing monomer shown in formula (I) provided by the present invention is not completely symmetrical, and may contain one or more epoxy groups and episulfide groups in one molecular structure.
The present invention also provides a photopolymer composition comprising:
the polymeric monomer includes the episulfide/epoxy writing monomer described above.
In the present invention, the content of the polymerizable monomer is preferably 20 to 40 parts by weight, more preferably 25 to 40 parts by weight, still more preferably 30 to 35 parts by weight, and most preferably 33 parts by weight; the polymerized monomer comprises the episulfide/epoxy writing monomer, can be one or more of the episulfide/epoxy writing monomers, can be all epoxy writing monomers when containing a plurality of episulfide writing monomers, can also be all episulfide writing monomers, and can also contain the epoxy writing monomers and the episulfide writing monomers simultaneously; in the present invention, the polymerizable monomer may contain polymerizable monomers of other structures in addition to the episulfide/epoxy writing monomer, and preferably further includes an acrylate monomer; the refractive index of the acrylate monomer is preferably equal to or greater than 1.5, more preferably equal to or greater than 1.52, still more preferably equal to or greater than 1.55, still more preferably equal to or greater than 1.57, and most preferably equal to or greater than 1.60; the acrylate monomer preferably comprises an aromatic group; the aromatic group is preferably one or more of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted fluorenyl; the substituent in the substituted phenyl, the substituted biphenyl, the substituted naphthyl and the substituted fluorenyl is preferably one or more of C1-C5 alkyl, hydroxyl, sulfydryl, C1-C5 alkoxy and C3-C5 heterocyclic radical independently; the heteroatom in the heterocyclic group is preferably nitrogen, oxygen or sulfur; the acrylate monomer preferably further comprises a halogen substituent; the halogen substituent is preferably chlorine or bromine; in the present invention, it is most preferable that, the acrylate monomer is 9,9-di (methyl acrylate) fluorene, phenyl acrylate, phenyl methacrylate, p-chlorophenyl acrylate, p-chlorophenyl methacrylate, p-bromophenyl acrylate, p-bromophenyl methacrylate, 2,4,6-trichlorophenyl acrylate, 2,4,6-trichlorophenyl methacrylate, 2,4,6-tribromophenyl acrylate, 2,4,6-tribromophenyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, pentabromobenzyl acrylate, pentabromobenzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenoxybenzyl methacrylate, and the like phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, 1,4-bis (2-thionaphthyl) -2-butyl acrylate, 1,4-bis (2-thionaphthyl) -2-butyl methacrylate, propane-2,2-diylbis [ (2,6-dibromo-4,1-phenylene) oxy (2- { [3,3,3-tris (4-chlorophenyl) propionyl ] oxy } propane-3,1-diyl) oxyethane-2,1-diyl ] diacrylate, bisphenol A dimethacrylate, tetrabromobisphenol A diacrylate, N-carbazole acrylate, and the like. The added high-refractive-index acrylate monomer can be subjected to free radical-cation hybrid photocuring with the episulfide/epoxy writing monomer, combines the advantages of free radical polymerization and cation polymerization, and shows a good synergistic effect. In view of improving diffraction efficiency, dimensional stability and refractive index modulation, the weight of the epoxy/episulfide writing monomer in the polymerized monomer is preferably 20% to 70%, more preferably 40% to 70%, even more preferably 50% to 70%, even more preferably 60% to 70%, and most preferably 66% to 67% of the weight of the polymerized monomer.
The content of the film forming agent is preferably 15 to 35 parts by weight, more preferably 20 to 30 parts by weight, still more preferably 20 to 25 parts by weight, and most preferably 22 parts by weight; the type of the film forming agent is not particularly limited in the invention, and the film forming agent is preferably a polymer or resin material with molecular weight of more than or equal to 1000 and certain adhesiveness; film formers having a lower refractive index are preferably used; the refractive index of the film forming agent is preferably 1.480 or less; more preferably, in the present invention, the film forming agent is one or more of vinyl acetate copolymer, cellulose ester, cellulose ether, polyvinyl alcohol, polyvinyl acetal, polyurethane, styrene-butadiene block copolymer and polyvinylpyrrolidone; wherein, the vinyl acetate copolymer is preferably one or more of homopolymers of vinyl acetate and acrylic ester, ethylene and styrene and homopolymers of vinyl acetate; the cellulose ester is preferably one or more of cellulose acetate, cellulose acetate-butyrate and cellulose acetate-butyrate; the cellulose ether is preferably one or more of methyl cellulose, ethyl cellulose and benzyl cellulose; the polyvinyl acetal is preferably polyvinyl butyral and/or polyvinyl formal; the polyurethane is obtained by reacting polyol and isocyanate, wherein the polyol is one or more of polytetrahydrofuran, polyethylene glycol, polypropylene glycol and castor oil; the isocyanate is preferably one or more of hexamethylene-1,6-diisocyanate, 1,4-cyclohexane diisocyanate and methyl-2,4-diisocyanate. In the present invention, the film forming agent of the present invention is most preferably one or more of cellulose acetate butyrate, polyvinylpyrrolidone, polyvinyl alcohol and polyvinyl acetate from the viewpoint of suppressing the dimensional shrinkage of the final grating product and improving the diffraction efficiency.
The photosensitive dye compound and the co-initiator together form a photoinitiator system in the photopolymer composition.
The content of the photosensitive dye compound is preferably 0.1 to 3 parts by weight, more preferably 0.1 to 1 part by weight, and still more preferably 0.1 to 0.5 part by weight; the photosensitive dye compound is preferably one or more of Irgacure 784, new methylene blue, thionine, basic Red 2, basic yellow, pinacyanol chloride, rhodamine 6G, betacyanin, ethyl Violet, victoria blue R, azurite blue, quinaldine Red, bright Green, basic orange G (astrazon orange G), da Luo Gong (darnow red), pyronin Y, rose Bengal, eosin Y, meldonone, 3,3' -carbonylbis (7-diethylaminocoumarin), iodonium pyrane (pyrilium I), diiodofluorescein, anthocyanidin, methylene blue, azurin A, crystal Violet (leucoonitril) and Caragave Green (leuconitrile).
The content of the coinitiator is preferably 0.5 to 3.5 parts by weight, more preferably 1 to 3 parts by weight, still more preferably 1.5 to 2.5 parts by weight, and most preferably 1.8 to 2 parts by weight; the coinitiator is preferably an initiating active compound containing an N atom, more preferably one or more of ethylenediamine, N-phenylglycine, 2- (4-chlorophenyl) -4,5-diphenylimidazole and ethyl 4-dimethyl-aminobenzoate.
According to the present invention, the photopolymer composition preferably further comprises 10 to 50 parts by weight of a solvent; mixing the composition by a solvent to form a homogeneous system; the content of the solvent is more preferably 20 to 50 parts by weight, still more preferably 30 to 50 parts by weight, still more preferably 40 to 50 parts by weight, and most preferably 43 to 45 parts by weight; in the present invention, the solvent is preferably a non-reactive solvent, more preferably one or more of a halogenated hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ester solvent, a hydrocarbon solvent and an amide solvent; among them, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, etc.; ketone solvents such as acetone, butanone, and the like; alcohol solvents such as ethanol, butanol, etc.; ester solvents such as ethyl acetate, butyl acetate, and the like; hydrocarbon solvents such as aliphatic hydrocarbon solvents or aromatic hydrocarbon solvents; amide solvents such as DMAC, DMF, and the like. Since having a low boiling point is advantageous for the subsequent coating film preparation process, it is preferable to use an organic solvent having a boiling point of 120 ℃ or less at normal pressure in the present invention. In the present invention, each of the above solvents may be used alone or as a mixed solvent of a plurality of solvents.
In the present invention, it is preferable to further include 0.1 to 5 parts by weight of other additives; other additives commonly used in the art, such as one or more of chain transfer agents, leveling agents, wetting agents, defoaming agents and tackifiers, as well as polyurethanes, thermoplastic polymers, other oligomers, compounds having additional functional groups (e.g., acetals, epoxides, oxetanes, oxazolines, dioxolanes), and/or compounds having hydrophilic groups (e.g., salts and/or polyethylene oxides), may be added as additional adjuvants and additives as long as the technical effects of the present invention are not affected.
The invention also provides a grating which is a resin film with a grating structure; the resin film is formed by curing the above-described photopolymer composition.
The invention also provides a preparation method of the grating, which comprises the following steps: s1) mixing the photopolymer composition to obtain a mixture; and S2) forming a film from the mixture and forming a grating structure to obtain the grating.
The above-mentioned photopolymer compositions are mixed to obtain a mixture, and in some particular embodiments of the invention, the mixture is obtained in the form of a melt or liquid by mixing said photopolymer compositions.
In the present invention, the composition may be mixed in proportion in an appropriate container, and a mechanical stirring or the like may be employed to make the mixing uniform, if any is necessary. The temperature of the mixing is not particularly limited, and in general, mixing under ambient conditions at room temperature or under heating (preheating) can be selected.
In other specific embodiments, the step of mixing may be performed under appropriate heating conditions. The heating temperature may be determined based on the activity of the components of the photopolymer composition and the desired viscosity of the system. Under some conditions it may be desirable to increase the mixing temperature to obtain a lower viscosity to obtain a blend in which the components are mixed uniformly. In addition, it is also desirable to control the degree of heating so as not to overheat, to avoid excessive polymerization in unnecessary process windows, which can cause difficulties in subsequent processing.
In some preferred embodiments of the invention, the temperature used in the step of mixing is above 10 ℃, more preferably above 30 ℃ and below 90 ℃, preferably below 60 ℃. The resulting mixed solution can be used immediately or stored briefly at the treatment temperature for use.
In addition, in order to prevent photo-curing during the mixing process, the operation of adding the photosensitive dye compound and the co-initiator should be performed at the end and operated in a dark room or a protective lamp environment inert to the photosensitive dye compound.
Forming a film on the mixture and forming a grating structure, preferably forming a film on a substrate by the mixture and forming the grating structure by exposure treatment; the exposure treatment preferably uses coherent light. In the present invention, this step is preferably embodied as follows: 1) The mixture is applied to a glass or high-transparency plastic film substrate in a dark room or in a protected lamp environment, using means known to those skilled in the art such as knife coating devices (doctor blades, knife rolls, curved bars (Commabar et al) or slit nozzles; 2) Standing to volatilize the solvent, and properly increasing the temperature for increasing the volatilization rate, or performing the volatilization at normal temperature and low pressure or in a blowing environment; 3) After the solvent is completely removed, covering another layer of glass substrate or high-transparency plastic protective film on the surface of the polymer film formed by the mixture, then cutting the polymer film into a proper size, and storing the polymer film in a dark place for later use to obtain a structure shown in figure 1; 4) Exposing the dry plate obtained in the step 3) in a double-beam light path by using laser interference (the light path is shown in figure 2) to form a holographic grating; a high laser intensity short exposure time mode is adopted; 5) And 4) irradiating the holographic polymer grating obtained in the step 4) by an LED lamp, a fluorescent lamp or an ultraviolet lamp until the holographic polymer grating is completely fixed and bleached.
In some embodiments of the invention, two beams of coherent light may be exposed simultaneously from one side of the polymer film (a transmissive grating); in other embodiments, two beams of coherent light are used to expose the polymer from both sides of the polymer film (reflective gratings).
In addition, the grating obtained by the invention can be a plane grating or a curved grating with a certain curvature. The method for producing the curved grating is not particularly limited, and in some specific embodiments, a film may be formed on a substrate having a curvature by using the substrate and exposing the substrate. In other embodiments, a planar substrate may be used, and the coating film may be processed into a curved grating with a certain curvature after exposure.
The invention also provides the application of the grating. Without limitation, the above-described gratings comprising photopolymer films of the present invention can be used in a variety of holographic display systems in the art, and can be used alone or in combination with other optical elements.
Further, the present invention provides a diffraction grating element for a holographic optical waveguide display system. The diffraction grating element includes a base layer and a photopolymer film layer. The photopolymer film layer is formed from a photopolymer composition; the substrate layer, the photopolymer composition is as described or defined above.
In some preferred embodiments, the grating elements are formed by sandwiching a layer of photopolymer film between a base layer and a protective layer. The photopolymer film layer is provided with at least two unconnected exposure areas, the exposure areas can be respectively or simultaneously exposed by a group of same coherent light sources, and after post-treatment, two areas with gratings are formed in one grating element.
The grating elements typically have a regular profile to facilitate use and installation, and may be in the shape of a strip, square or circular disk.
In some preferred embodiments, the grating element of the present invention has the shape of a long strip, and has exposure regions subjected to exposure or the like at both end regions in the length direction of the long strip, and a grating (holographic recording) structure is formed in each exposure region. And the two exposure areas are physically unconnected. Typically, one exposure area may be used as an incoupling grating area, and the other exposure area may be used as an outcoupling grating area.
The grating element of the present invention can be used in a holographic optical waveguide display device, and is particularly suitable for head-up devices (e.g., AR display glasses devices, etc.) of Augmented Reality (AR) that has strict requirements for diffraction efficiency, refractive index modulation, light transmittance, and the like, and head-up displays (HUDs) of automobiles or aircraft.
To further illustrate the present invention, a photopolymer composition, an episulfide/epoxy writing monomer and a grating provided by the present invention are described in detail below with reference to the examples.
The method for obtaining the episulfide compound used in the following examples is not particularly limited, and commercially available products can be used or synthesized by a known method (EP 2799455, EP0761665, JP 3491660), and the remaining reagents are commercially available.
Example 1
Compound 1 (Z and Z' are both S), 9,9-bis (carbomethoxy) fluorene, butyl acetate as solvent, cellulose acetate butyrate as film former, N-phenylglycine as initiator and 2- (4-chlorophenyl) -4,5-diphenylimidazole were added to a sample vial, stirred at room temperature until completely clear, and then dye eosin Y was added in the dark or red and stirred for 30min to obtain a uniformly clear photopolymer solution (all component ratios are shown in the table below, for example). And then coating the mixed solution on a glass substrate with the thickness of 1mm in dark or red light, wherein the coating thickness is about 20 mu m, horizontally standing, covering a TAC protective film with the thickness of 40 mu m on the surface after the dye is completely volatilized, and obtaining the photopolymer dry plate. The resulting dry plate had an energy density of 15mJ/cm in the dual beam path as shown in FIG. 2 2 The 532nm laser is subjected to interference exposure, and the reflection type holographic grating is formed after the reflection type holographic grating is subjected to fixation bleaching for about 30min through irradiation of a green LED lamp.
The diffraction efficiency of the reflective holographic grating obtained in example 1 was tested, using a 532nm LED green spot light source as a test light source, using a turntable to change the angle between the grating and the test beam, and testing the relative diffraction efficiency at different angles to obtain a grating diffraction efficiency curve, as shown in fig. 3. As can be seen from fig. 3, the reflection type hologram grating obtained in this example has a diffraction efficiency of more than 99%, a large angular selectivity, and a refractive index modulation degree of more than 0.04.
Example 2
Compound 2 (Z is S), compound 3 (Z and Z' are both S), butyl acetate solvent, cellulose acetate butyrate as film-forming agents, N-phenylglycine as initiator and 2- (4-chlorophenyl) -4,5-diphenylimidazole were added to a sample bottle, and after stirring at room temperature until they were completely clear, dye eosin Y was added in the dark or red and stirred for 30min to obtain a uniformly clear photopolymer solution (all component ratios are shown in the table below, for example). And then coating the mixed solution on a glass substrate with the thickness of 1mm in dark or red light, wherein the coating thickness is about 20 mu m, horizontally standing, and covering a TAC protective film with the thickness of 40 mu m on the surface after the dye is completely volatilized to obtain the photopolymer dry plate. The resulting dry plate had an energy density of 15mJ/cm in the dual beam path as shown in FIG. 2 2 The 532nm laser is subjected to interference exposure, and the reflection type holographic grating is formed after the reflection type holographic grating is subjected to fixation bleaching for about 30min through irradiation of a green LED lamp.
| Composition of | Mass content of |
| Eosin Y | 0.2％ |
| N-phenylglycine | 0.8％ |
| 2- (4-chlorophenyl) -4,5- |
1 |
| Compound | |
| 2 | 22 |
| Compound | |
| 3 | 11％ |
| Cellulose acetate butyrate | 22％ |
| Acetic acid butyl ester | 43％ |
The diffraction efficiency of the reflective holographic grating obtained in the embodiment 2 is tested, an LED green spot light source of 532nm is used as a test light source, an included angle between the grating and a test beam is changed by using a turntable, and the relative diffraction efficiency at different angles is tested, so that the reflective grating obtained in the embodiment has the diffraction efficiency of more than 95%, the angle selectivity is high, and the refractive index modulation degree can reach 0.06.
Comparative example 1
9,9-bis (methyl acrylate) fluorene, solvent butyl acetate, film forming agent cellulose acetate butyrate, initiator N-phenylglycine and 2- (4-chlorophenyl) -4,5-diphenylimidazole are added into a sample bottle, and after stirring at normal temperature until the solution is completely clear, dye eosin Y is added under the condition of keeping out light or red light and stirring is carried out for 30min to obtain a uniform clear photopolymer solution (all component ratios are shown in the following table). The mixed solution is subsequently applied to a glass 1mm thick in the dark or under red lightAnd coating a TAC protective film with the thickness of 40 mu m on the surface of the glass substrate after the dye is completely volatilized by horizontal standing, thereby obtaining the photopolymer dry plate. The resulting dry plate had an energy density of 15mJ/cm in the dual beam path as shown in FIG. 2 2 The 532nm laser is subjected to interference exposure, and the reflection type holographic grating is formed after the reflection type holographic grating is subjected to fixation bleaching for about 30min through irradiation of a green LED lamp.
| Composition of | Mass content |
| Eosin Y | 0.2％ |
| N-phenylglycine | 0.8％ |
| 2- (4-chlorophenyl) -4,5- |
1％ |
| 9,9-bis (carbomethoxy) fluorene | 30％ |
| Cellulose acetate butyrate | 22％ |
| Acetic acid butyl ester | 46％ |
The diffraction efficiency of the reflective holographic grating obtained in comparative example 1 was tested by the same method as in example 1, and a grating diffraction efficiency curve was obtained, as shown in fig. 3. As can be seen from fig. 3, the diffraction efficiency of the reflection grating obtained in comparative example 1 was about 88%, and the refractive index modulation degree was about 0.02.
Claims (3)
1. A photopolymer composition comprising:
the polymerized monomer comprises one or more episulfide/epoxy writing monomers shown as compounds 1 to 3:
z and Z' are each independently S or O;
and at least one of Z and Z' comprises S;
the refractive index of the episulfide/epoxy writing monomer is more than or equal to 1.60;
the polymerized monomers also comprise acrylate monomers; the weight of the epoxy/episulfide writing monomer in the polymerized monomer is 20 to 70 percent of the weight of the polymerized monomer.
2. The photopolymer composition of claim 1 further comprising 10 to 50 parts by weight of a solvent and 0.1 to 5 parts by weight of other additives;
the film forming agent is selected from one or more of vinyl acetate copolymer, cellulose ester, cellulose ether, polyvinyl alcohol, polyvinyl acetal, polyurethane, styrene-butadiene block copolymer and polyvinylpyrrolidone;
the photosensitive dye compound is selected from one or more of Irgacure 784, new methylene blue, thionine, basic Red 2, basic yellow, pinacyanol chloride, rhodamine 6G, betacyanin, ethyl violet, victoria blue R, azure blue, quinaldine Red, brilliant green, basic orange G, da Luo Gong, pyronin Y, rose bengal, eosin Y, michler's ketone, 3,3' -carbonylbis (7-diethylaminocoumarin), iodopyrum, diiodofluorescein, anthocyanin, methylene blue, azure A, crystal violet and malachite green;
the coinitiator is one or more selected from ethylenediamine, N-phenylglycine, 2- (4-chlorphenyl) -4,5-diphenyl imidazole and 4-dimethyl-ethyl aminobenzoate.
3. A grating, characterized in that the grating is a resin film having a grating structure; the resin film is formed by curing the photopolymer composition of claim 1 or 2.
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