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WO2019078585A1 - Composé à base de fluor non réactif et composition photopolymérisable le comprenant - Google Patents

Composé à base de fluor non réactif et composition photopolymérisable le comprenant Download PDF

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Publication number
WO2019078585A1
WO2019078585A1 PCT/KR2018/012194 KR2018012194W WO2019078585A1 WO 2019078585 A1 WO2019078585 A1 WO 2019078585A1 KR 2018012194 W KR2018012194 W KR 2018012194W WO 2019078585 A1 WO2019078585 A1 WO 2019078585A1
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Prior art keywords
carbon atoms
acrylate
compound
isocyanate
group
Prior art date
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Ceased
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PCT/KR2018/012194
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English (en)
Korean (ko)
Inventor
장석훈
김헌
김부경
장영래
허용준
권세현
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Priority claimed from KR1020180122648A external-priority patent/KR102268129B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2020541633A priority Critical patent/JP7005100B2/ja
Priority to CN201880067514.5A priority patent/CN111247121B/zh
Priority to US16/756,072 priority patent/US11292888B2/en
Publication of WO2019078585A1 publication Critical patent/WO2019078585A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component

Definitions

  • the present application claims the benefit of priority based on Korean Patent Application No. 10-2017-0134212, October 16, 2017, and Korean Patent Application No. 201-20-0122648, October 15, 2018, The entire contents of which are incorporated herein by reference.
  • the present invention relates to a non-bioactive fluorine compound having a specific chemical structure, a photopolymerizable composition containing the same, a hologram recording medium, an optical element, and a recording method of a hologram.
  • a holographic recording medium (medium) generates a diffraction grating in the hologram recording layer through an exposure process, reads a change in refractive index in the recorded medium, and reads information.
  • a photopolymer photopolymer can easily store an optical interference pattern in a hologram by photopolymerization of a low molecular monomer, it can be used as an optical lens, a mirror, a deflection mirror, a filter, a diffusing screen, a diffraction member, a light guide, A holographic optical element having functions of a mask and / or a mask, a medium of an optical memory system and a light diffusing plate, an optical wavelength splitter, a reflection type, and a transmission type color filter.
  • the photopolymerizable composition for producing a hologram comprises a polymeric binder, a monomer, and a photoinitiator, and irradiates the photosensitive film containing the hologram recording layer prepared from such a composition with laser interference light to induce photopolymerization of the optional monomer.
  • the polymerized portion has a higher refractive index than that of the non-polymerized portion, resulting in a refractive index modulation, and by this refractive index modulation A diffraction grating is generated.
  • the refractive index modulation value n is influenced by the thickness of the photopolymerizable layer and diffraction efficiency (DE), and the angle selectivity becomes wider as the thickness becomes thinner.
  • DE diffraction efficiency
  • various attempts have been made to manufacture a photopolymerizable layer having a small thickness and a large refractive index modulation value, along with a demand for development of a material capable of maintaining a high diffraction efficiency and a stable hologram.
  • the present invention aims to provide a non-reactive fluorinated compound having a specific chemical structure.
  • the present invention also provides a hologram recording medium including a photopolymerizable layer having a small thickness and a high refractive index modulation value.
  • the present invention also provides an optical element including a hologram recording medium.
  • the present invention also provides a holographic recording method comprising selectively polymerizing a photo-polymerizable monomer contained in the photopolymerizable composition by electromagnetic radiation.
  • the present invention provides a non-bioactive fluorinated compound represented by the following general formula (1) or (2).
  • R1 and R2 each represent a terminal blocking group and are independently the same or different and each is an alkyl ester group having 1 to 10 carbon atoms or an alkyl ether group having 1 to 10 carbon atoms which is substituted or unsubstituted with a halogen atom;
  • a and B are a single bond or an alkylene group having 1 to 5 carbon atoms
  • R3 to R6 each independently represent hydrogen, a halogen atom or an alkyl group having 1 to 5 carbon atoms, at least one of R3 to R6 is a fluorine atom,
  • n1 to n3 are each an integer of 1 to 5, and X is an alkylene group having 1 to 10 carbon atoms or an alkyl ether group having 1 to 10 carbon atoms.
  • a hologram recording layer formed by the photopolymerizable composition is provided.
  • the present specification also provides an optical element including the above-described hologram recording medium. Further, the present specification discloses a method for producing a hologram recording medium, which comprises irradiating actinic radiation to the above-mentioned hologram recording medium to selectively polymerize the photo- A hologram recording method is provided.
  • (meth) acrylate is used as a concept including both methacrylate and acrylate.
  • hologram means a recording medium on which optical information is recorded in the entire visible range and the near-ultraviolet range (300 to 800 nm) through an exposure process, for example, in-line Gabor), a hologram, an off-axis hologram, a pre-aperture holographic hologram, a white light transmission hologram ("rainbow hologram”), a Denisyuk hologram, a biaxial hologram, Is used as a concept that includes both a visual hologram such as an edge-literature hologram or a holographic stereogram.
  • a non-bioactive fluorine compound represented by the following general formula (1) or (2).
  • R 1 and R 2 are each a terminal blocking group and are each independently the same or different and is an alkyl ester group having 1 to 10 carbon atoms or an alkyl ether group having 1 to 10 carbon atoms which is substituted or unsubstituted with a halogen atom,
  • a and B are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms
  • R3 and R6 are the same or different and are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, R3 Lt; 6 > is a fluorine atom,
  • n1 to n3 are the number of repetition of repeating units and are an integer of 1 to 5
  • X is alkylene having 1 to 10 carbon atoms
  • black is alkylene group having 1 to 10 carbon atoms.
  • non-bioactive means that the compound is not compatible with an acrylate-based polyol, an isocyanate, and a photopolymerizable monomer.
  • alkyl ether group having 1 to 10 carbon atoms is used as a concept including both an alkoxy group (Alkyl-O-) and an alkylene oxide repeating unit (-Alkylene-O-).
  • Such compounds may have a refractive index of less than about 1.45, preferably from about 1.30 to about 1.45, more preferably from about 1.30 to about 1.40, or from about 1.35 to about L40, Lt; / RTI > And, the compound may have a molecular weight of about 300 or more, more preferably about 300 to about 1,000, or about 550 to about 800.
  • R3 to R6 are each independently the same or different from each other and represent hydrogen, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, of which at least half consists of a fluorine atom.
  • the above-mentioned non-bio-reactive fluorinated compound is preferably a compound represented by the formula
  • the non-bioerogical fluorine compound has a fluorine substituent on the carbon constituting the ethylene glycol repeating unit in a form containing an ethylene glycol repeating unit and a blocking group at the terminal.
  • These compounds may be prepared by reacting mono-, di-, tri-, tetra- or penta-ethyleneglycol containing 1 to 5 ethylene glycol repeating units containing fluorine as precursors, Can be made through a catalytic reaction that introduces a terminal blocking group into the hydroxy group of the compound.
  • the temperature for introducing the ester group or the ether group into the blockade, the catalyst, and the like can be employed without any limitations that are generally used in the technical field to which the present invention belongs.
  • an ester group is introduced into a terminal blocking group
  • an acyl chloride compound and trimethylamine can be bonded using a base.
  • a photoinitiator may be provided.
  • the present inventors have found that a hologram formed from a photopolymerizable composition comprising a polymer matrix formed from a specific acrylate-based polyol and an isocyanate compound as described above exhibits greatly improved refractive index modulation values and diffraction efficiencies
  • a hologram formed from a photopolymerizable composition comprising a polymer matrix formed from a specific acrylate-based polyol and an isocyanate compound as described above exhibits greatly improved refractive index modulation values and diffraction efficiencies
  • the above-described non-protonic fluorine compound in addition to the matrix component, by maximizing the difference in refractive index between the exposed portion and the non-exposed portion, sensitivity to recording light is increased , And thus the recording efficiency can be remarkably increased.
  • the polymer matrix may serve as a support for the final product, such as the photopolymerizable composition and the film produced therefrom,
  • the refractive index can serve as a portion having a different refractive index to enhance the refraction.
  • the polymer matrix may include a copolymerization product between an acrylate-based polyol and a compound containing at least one isocyanate group.
  • the precursor of the polymer matrix may include a monomer or an oligomer forming the polymer matrix, and specifically, a compound containing the acrylate-based polyol and at least one isocyanate group.
  • the acrylate-based polyol is preferably an alkyl acrylate having an alkyl group having 1 to 5 carbon atoms; And a repeating unit derived from a hydroxyalkyl acrylate having 1 to 5 carbon atoms in the alkyl group, and having an OH equivalent of about 1000 to about 2000 g / md and a weight average molecular weight of about 600,000 To about 800,000.
  • alkyl acrylate component having 1 to 5 carbon atoms in the alkyl group as the monomer for constituting the above acrylate repeating unit examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, and pentyl (meth) acrylate.
  • hydroxyalkyl acrylate monomer having 1 to 5 carbon atoms in the alkyl group examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) .
  • the hydroxyalkyl acrylate may be used in an amount of about 1 to about 15 parts by weight based on 100 parts by weight of the alkyl acrylate in view of controlling the OH equivalent of the polyol, It may be most desirable to use as part.
  • the compound containing at least one isocyanate group may be a known compound having an average of at least one NCO functional group per molecule or a condensate thereof, And may be a compound containing at least one isocyanate group.
  • the isocyanate compound may be an aliphatic, cycloaliphatic, aromatic or aromatic aliphatic mono-isocyanate di-isocyanate, tri-isocyanate or poly-isocyanate; Or oligo- isocyanates of diisocyanates or triisocyanates having urethane, urea, carbodiimide, acyl urea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazine dione structures Or poly-isocyanate.
  • the compound containing at least one isocyanate group include at least one compound selected from butanetriene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatoethyl ) Octane, 2,2,4- and / or 2,4,4-trimethylnucleosamethylene diisocyanate, isomeric bis (4,4'-isocyanatocyclohexyl) methane and any of its common compound, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexane nucleus xylene diisocyanate, isomers cycloalkyl nucleic acid di-diisocyanate, 1,4-phenylene diisocyanate, 2,4-and / Or 2,6- can be reacted with a diene compound such as rubrene diisocyan
  • the polyol that forms the polymer matrix by counteracting the compound containing at least one isocyanate group may further include other diols, triols or polyols in addition to the acrylate-based polyols described above. More specifically, polyols which form a polymer matrix by reaction with a compound containing at least one isocyanate group, include aliphatic aromatic diols, triols or polyols having 2 to 20 carbon atoms; An alicyclic diol having 4 to 30 carbon atoms, a triol or a polyol, and an aromatic diol, a triol or a polyol having 6 to 30 carbon atoms.
  • the isocyanate compound in view of the matrix crosslinking control of the polyol component and the isocyanate component, may be used in an amount of about 5 to about 50 parts by weight based on 100 parts by weight of the acrylate-based polyol, About 10 to about 30 parts by weight may be used.
  • the photopolymerizable composition may further include a polyol other than the acrylate-based polyol to more easily control the crosslinking point in the polymer matrix of the hologram and further increase the degree of crosslinking of the polymer matrix.
  • the hologram produced from the photopolymerizable composition of this embodiment can have a high refractive index modulation value and diffraction efficiency even in a thin thickness range.
  • diols examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4- Glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, diethyloctanediol positional isomer, 1,3-butylene glycol, a cyclic nucleic acid diol, 1,4-cyclohexanedic acid dimethanol, , 1,2- and 1,4-cyclohexanediyl, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 2,2- Dimethyl-3-hydroxypropionate.
  • triols examples include trimethyl ether, trimethylol propane, and glycerol.
  • Suitable highly functional alcohols are ditrimethyl propane, pentaerythritol, dipentaerythritol or sorbic acid.
  • the polyol also includes aliphatic and cycloaliphatic polyols of relatively high molecular weight, such as polyester polyols, such as polyether polyols, polycarbonate polyols, hydroxy-functional acrylic resins, hydroxy-functional polyurethanes, Functional epoxy resin and the like can be used.
  • polyester polyols such as polyether polyols, polycarbonate polyols, hydroxy-functional acrylic resins, hydroxy-functional polyurethanes, Functional epoxy resin and the like can be used.
  • the polyester polyol may be, for example, ethanediol, di-, tri- or tetraethylene glycol, 1,2-propanediol, di-, tri- or tetrapropyleneglycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-nucleic acid diol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclo- , 1,4-dimethylolcyclo-nucleic acid, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or a mixture thereof, optionally using tri-
  • higher functional polyols such as glycine
  • other polyols such as succinic acid, glutaric acid, adipic acid, pimelic
  • di- and polyhydroxy compounds of cyclic aliphatic and / or aromatic are also suitable as polyhydric alcohols for the preparation of polyester polyols.
  • the free polycarboxylic acid it is also possible to use a polycarboxylic acid anhydride or polycarboxylate of lower alcohol or a polycarboxylate thereof, or a mixture thereof, in the production of polyester.
  • Polyester polyols that can be used in the synthesis of the polymer matrix also include mono- or copolymers of lactones, which are preferably lactones such as butyrolactone, epsilon -caprolactone and / or methyl- epsilon -caprolactone Or with a suitable bifunctional and / or higher functional initiator molecule, such as the above-mentioned small molecular weight polyhydric alcohols, for example, polyester polyesters as lactosynthesis components.
  • lactones which are preferably lactones such as butyrolactone, epsilon -caprolactone and / or methyl- epsilon -caprolactone Or with a suitable bifunctional and / or higher functional initiator molecule, such as the above-mentioned small molecular weight polyhydric alcohols, for example, polyester polyesters as lactosynthesis components.
  • the polycarbonate having a hydroxyl group is also suitable as a polyhydroxy component for prepolymer synthesis, for example, a diol such as 1,4-butanediol and / or 1,6-nucleic acid diol and / or 3-methyl
  • a diol such as 1,4-butanediol and / or 1,6-nucleic acid diol and / or 3-methyl
  • diaryl carbonates such as diphenyl carbonate, dimethyl carbonate or phosgene.
  • the polyether polyol which can be used for the synthesis of the polymer matrix may be, for example, a polyaddition product of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide and epichlorohydrin, Those obtained by polycondensation of polyhydric alcohols and polyhydric alcohols, amines and amino alcohols obtained by condensation of condensation products and graft products, and polyhydric alcohols or condensates thereof.
  • the polyether polyols include a number-average molecular weight of between 1.5 and 6 and an OH functionality of 200 to 18000 g / mole, preferably an OH functionality of 1.8 to 4.0 and a number-average molecular weight of 600 to 8000 g / mole , Particularly preferably an OH functionality of from 1.9 to 3.1 and a number average molecular weight of from 650 to 4500 g / mol, Poly (propylene oxide), poly (ethylene oxide), and combinations thereof, or poly (tetrahydrofuran) in the form of block copolymers, and mixtures thereof.
  • the photopolymerizable composition includes a non-reactive fluorinated compound represented by the following general formula (1) or (2).
  • R @ 2 is a group of formula --NR @ 2 R @ 2,
  • the end capping groups each independently represent the same or differently, halogen atoms, substituted or unsubstituted, an ether group in the alkyl group having 1 to 10 carbon atoms or an alkyl ester group having 1 to 10 carbon atoms in the, "
  • a and B are a single bond or an alkylene group having 1 to 5 carbon atoms
  • R3 to R6 each independently represent hydrogen, a halogen atom or an alkyl group having 1 to 5 carbon atoms, at least one of R3 to R6 is a fluorine atom,
  • n1 to n3 each represent a repetition number of repeating units each of which is an integer of 1 to 5;
  • X is alkylene of 1 to 10 carbon atoms; and
  • black is alkylene group of 1 to 10 carbon atoms.
  • the sensitivity to recording light can be increased, and thus the recording efficiency can be remarkably increased.
  • the non-reactive fluorinated compound may have a refractive index of less than about 1.45, preferably about L30 to about 1.45, more preferably about
  • the non-bio-reactive fluorine compound may be prepared by reacting the acrylate- Can serve to improve the dispersibility and flexibility of the isocyanate-based polymer matrix. That is, since the non-reactive fluorinated compound has no reactivity with respect to acrylate-based polyesters, isocyanates and other photoreactive monomers, the non-reactive fluorinated compounds may exist in the matrix while maintaining their inherent properties. Can be appropriately controlled so as to improve the photopolymerization efficiency at the time of exposure.
  • the photoreactive monomer may include a polyfunctional (meth) acrylate monomer or a monofunctional (meth) acrylate monomer.
  • the monomer is polymerized to increase the refractive index at a portion where the polymer is relatively present, and at the portion where the polymer binder is relatively present, the refractive index is relatively lowered, , And the diffraction grating is generated by such refractive index modulation.
  • Examples of the photoreactive monomer include polyfunctional (meth) acrylate monomers having a refractive index of 1.5 or more.
  • the multifunctional (meth) acrylate monomers having a refractive index of 1.5 or more include halogen atoms (bromine, iodine, etc.) ), Phosphorus (P), or an aromatic ring.
  • Is not less than the refractive index of 1.5-functional (meth) acrylate monomer A more specific example of a "roneun bisphenol A modified diacrylate series, fluorene acrylate-based, bisphenol fluorene epoxy acrylate-based (such as HR6100, HR6060, HR6042 - Miwon ⁇ ), Halogenated epoxy acrylate series (HR1139, HR3362, etc. - Miwon).
  • Another example of the above photo-labile monomers includes monofunctional (meth) acrylate monomers.
  • the monofunctional (meth) acrylate monomer may include an ether bond and a fluorene functional group in the molecule.
  • the monofunctional (meth) acrylate monomer examples include phenoxybenzyl (meth) acrylate, (meth) acrylate, benzyl (meth) acrylate, 2- (phenylcyano) ethyl (meth) acrylate, or biphenylmethyl (meth) acrylate.
  • the optically maleic monomer may have a weight average molecular weight of 50 to 1000, or 200 to 600.
  • the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by GPC method.
  • the photopolymerizable composition of the embodiment includes a photoinitiator.
  • the photoinitiator is a compound that is activated by light or actinic radiation and initiates polymerization of a compound containing a photoactive functional group, such as the photo-labile monomer.
  • photoinitiator conventionally known photoinitiators can be used without any limitation, and specific examples thereof include a photo radical polymerization initiator and a photo cationic polymerization initiator. .
  • photoradical polymerization initiator examples include imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, And derivatives thereof.
  • examples of the photo-radical polymerization initiator include 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone, 2-mercapto benzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1 -one (product name: Irgacure 651 1 manufactured by BASF) -ketone (product name: Irgacure 184 7 manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: Irgacure 369 / , 4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-phenyl) titanium (product name: Irgacure 784, manufactured by
  • Examples of the cationic ion-generating initiator include diazonium salts, sulfonium salts, and iodonium salts, and examples thereof include sulfonic acid esters, imidosulfonates, dialkyl- ( ⁇ 6-benzene) ( ⁇ 5-cyclopentadienyl) iron ( ⁇ ), and the like can be given as examples of the silane-aluminum complex. Also, benzoin tosylate, 2,5-dinitrobenzyl tosylate, n-tolylphthalic acid imide and the like can be mentioned.
  • the cationic polymerization More specific examples of the initiator include Cyracure UVI-6970, Cyracure UVI-6974 and Cyracure UVI-6990 (manufactured by Dow Chemical Co. in USA), Irgacure 264 and Irgacure 250 (manufactured by BASF) or CIT-1682 Soda) and the like.
  • the photopolymerizable composition of this embodiment may contain one molecule (Type I)
  • Type [pi] initiator may also be used.
  • (Type I) systems for such free radical photopolymerisation are, for example, aromatic ketone compounds in combination with tertiary amines such as benzophenone, alkylbenzophenone, 4,4'-bis (dimethylamino) benzophenone (Michler's ) ≪ / RTI > ketones), anthrone and halogenated benzophenone or mixtures of this type.
  • bis (type ⁇ ) initiator examples include benzoin and derivatives thereof, benzyl ketal, acylphosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, phenylglycine (4-phenylthio) phenyl] octane-1,2-dione 2- (0-benzoyloxime) and alpha-aminopyrimidine -Hydroxyalkylphenone, and the like.
  • acylphosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • bisacylphosphine oxide phenylglycine (4-phenylthio) phenyl] octane-1,2-dione 2- (0-benzoyloxime)
  • alpha-aminopyrimidine -Hydroxyalkylphenone alpha-aminopyrimidine -Hydroxy
  • the photopolymerizable composition comprises A) a polymer matrix or precursor thereof
  • a photoinitiator of about 0.1 to about 10 parts by weight 0 / may include, preferably, the polymer matrix or precursor thereof from about 30 to about 70 parts by weight 0/0; The non-fluorine-based compound male half about 5 to about 35 parts by weight 0/0, the male flare monomer, about 20 to about 60 weight 0/0; And from about 0.1% to about 10% by weight of a photoinitiator.
  • the photopolymerizable composition when the photopolymerizable composition further comprises an organic solvent, the content of the above-mentioned components is based on the total of these components (the sum of the components excluding the organic solvent).
  • the photopolymerizable composition may further include a plasticizer.
  • the plasticizer may play a role of controlling the melting point, flexibility, toughness, diffusion degree of the monomer, and processability of each component contained in the composition.
  • Such plasticizers specifically include, for example, polyalkyl ether plasticizers including phthalate plasticizer : poly (ethylene oxide) methyl ether and the like, including dibutyl phthalate and the like, An alkylamide-based plasticizer containing ⁇ , N-dimethylformamide and the like, a cyclic nucleic acid dicarboxylic acid-based plasticizer including a cyclic nucleic acid dicarboxylic acid diisononyl ester, a phosphorus plasticizer including tributyl phosphate, And a citrate-based plasticizer.
  • the plasticizer is distinguished from the solvent in that it remains in the holographic storage medium and controls the physical properties of each polymer component.
  • the above-described non-biofunctional fluorine compound and plasticizer component can improve the flexibility of a polyurethane-based polymer matrix having a specific structure formed by the reaction of an acrylate-based polyol and an isocyanate, and in particular, It is possible to maximize the dispersibility of the photo-labile monomer in the photopolymerizable monomer and to directly increase the contrast of the hologram formed by diffusing into the vacancy in the interference pattern without directly participating in the polymerization of the photo- .
  • the photopolymerizable composition may further include a photo-sensitizing dye.
  • the photo-sensitizing dye acts as an enhancer dye for increasing or decreasing the photoinitiator. More specifically, the photoinitiator dye is stimulated by light irradiated to the photopolymer composition to serve as an initiator for initiating polymerization of the monomer and the crosslinking monomer can do.
  • the photopolymerizable composition is a light sensitive dye 0.01. To 30 it can be included by weight 0/0, or from 0.05 to 20 parts by weight 0/0.
  • the examples of the photosensitive dye are not limited to a wide variety, and a variety of commonly known compounds can be used.
  • Specific examples of the light-sensitive dye include sulfonium derivatives of ceramidonine, new methylene blue, thioerythrosine triethylammonium, 6-acetylamino-2-methylserine But are not limited to, 6-acetylamino-2-methylceramidonin, eosin, erythrosine, rose bengal, thionine, baseic yellow, Pinacyanol chloride ), Rhodamine 6G, gallocyanine, ethyl violet, Victoria blue R, Celestine blue, QuinaldineRed : Crystal violet, (crystal violet), Brilliant Green (Brilliant Green), AstraZone (GI), orange G (dark red), pyronin Y, basic red 29, pyrylium iodide, safranin O, Cyanine, methylene blue, Azure A, or
  • the photopolymerizable composition may further include an organic solvent.
  • organic solvent include ketones, alcohols, acetates and ethers, and mixtures of two or more thereof.
  • Such an organic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butane, i-butanol or t-butanol; Ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers of tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more of these.
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone
  • Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butane, i-butanol or t-butan
  • the organic solvent may be added to the photopolymerizable composition at the time when the respective components contained in the photopolymerizable composition are mixed, or may be added to the photopolymerizable composition while the components are dispersed or mixed in the organic solvent. If the content of the organic solvent in the photopolymerizable composition is too small, the flowability of the photopolymerizable composition may be lowered, resulting in defects such as streaks in the finally produced film. Also, when the organic solvent is excessively added, the solid content is lowered, and the coating and film formation are not layered, so that the physical properties and surface properties of the film may be deteriorated, and defects may occur during the drying and curing process . have. Accordingly, the photopolymerizable composition is a concentration of the total solid content of 1% to 70 parts by weight 0/0 by weight of the components contained or 2 to
  • the photopolymerizable composition may further include other additives, a catalyst, and the like.
  • the photopolymerizable composition may comprise a catalyst commonly known for promoting polymerization of the polymer matrix or the photo-labile monomer.
  • the catalyst include tin octanoate, zinc octanoate, dibutyltin dilaurate, dimethylbis [0-oxoneodecyl) oxy] stannane, dimethyltin dicarboxylate, zirconium bis Eate), zirconium acetylacetonate or tertiary amines such as 1,4-diazabicyclo [2.2.2] octane, Diazabicyclo- nonane, diazabicyclo- decane, 1,1,3,3-tetramethylguanidine, 1,3,4,6,7,8-Nucleic acid hydro-1-methyl-2H-pyrimido (1,2 -a) pyrimidine, and the like.
  • the use of the photopolymerizable composition of this embodiment can provide a hologram that can achieve a significantly improved refractive index modulation value and a high diffraction efficiency compared to a previously known hologram having a thinner thickness.
  • the hologram recording medium can realize a refractive index modulation value (n) of 0.009 or more or 0.010 or more even at a thickness of 30 to 30 nm.
  • the remaining components except for the compound containing at least one isocyanate group forming the polymer matrix or its precursor are homogeneously homogenized and mixed, and the compound containing at least one isocyanate group is later mixed with the catalyst to form a hologram You can prepare for the course.
  • the photopolymerizable composition according to one embodiment of the present invention can be used without any limitation, such as a conventionally known stirrer, a stirrer, or a mixer, and the temperature in the mixing process is preferably 0 to 100 ° C it may be 10 to 80 ° C, particularly preferably 20 to 60 ° C.
  • the remaining components other than the compound containing at least one isocyanate group forming the polymer matrix or its precursor are first homogeneously homogenized and mixed, and then, at the time of adding the compound containing at least one isocyanate group,
  • the composition may be a liquid formulation that is cured at a temperature of 20 or more.
  • the photopolymerization may be injected into a predetermined substrate or mold or coated.
  • a method of introducing a visual hologram to a hologram recording medium manufactured from the photopolymerizable composition can be used without any limitations in a conventionally known method, and the method described in the holographic recording method of the embodiment to be described later is adopted as an example .
  • a recording method of a hologram comprising the step of selectively irradiating the hologram recording medium with actinic radiation to selectively polymerize the optically maleic monomer.
  • a visual hologram can be recorded on media provided through the process of shaking and curing the photopolymerizable composition, using known devices and methods under commonly known conditions.
  • an optical element including a hologram recording medium can be provided.
  • the optical element include a holographic optical element having a function of an optical lens, a mirror, a deflecting mirror, a filter, a diffusion screen, a diffraction member, a light guide, a waveguide, a projection screen and / A diffusion plate, a light wavelength splitter, a reflection type, and a transmission type color filter.
  • An example of an optical element including a commercial hologram recording medium is a hologram display device.
  • the hologram display device includes a light source unit, an input unit, an optical system, and a display unit.
  • the light source unit irradiates a laser beam used for providing, recording, and reproducing three-dimensional image information of an object in an input unit and a display unit.
  • the input unit is a part for preliminarily inputting three-dimensional image information of an object to be recorded on the display unit.
  • three-dimensional information of an object such as the intensity and phase of light by space is stored in an electrically driven liquid crystal SLM Can be input, and the input range can be used at this time.
  • the optical system may include a mirror, a polarizer, a universal splitter, a pan shutter, a lens, and the like.
  • the optical system includes an input beam for transmitting a laser beam emitted from the light source unit to an input unit, It can be distributed by starting.
  • the display unit receives three-dimensional image information of an object from an input unit, records the three-dimensional image information on an hologram plate composed of an optically addressed SLM (SLM), and reproduces a three-dimensional image of the object.
  • SLM optically addressed SLM
  • the three-dimensional image information of the object can be recorded through the interference between the input beam and the reference beam.
  • the three-dimensional image information of the object recorded on the hologram plate can be reproduced as a three-dimensional image by the diffraction pattern generated by the read beam, and the erase beam can be used to quickly remove the formed diffraction pattern.
  • the hologram plate can be moved between a position at which the 3D image is input and a position at which the 3D image is reproduced.
  • a photopolymerizable composition capable of more easily providing a hologram recording layer having a thin thickness and a greatly improved refractive index modulation value and a high diffraction efficiency, a hologram recording medium including a hologram recording layer formed by the composition , An optical element including the hologram recording medium, and selectively polymerizing the photopropionic monomer contained in the composition by actinic radiation.
  • the 589 nm refraction of the liquid product was measured to be 1.37 using an Abbe refractometer.
  • a plasticizer tributyl phosphate, TBP, Sigma Aldrich
  • a photo-polymerizable monomer (1 to 2 functional acrylate, HR6042, MIWON, refractive index: 1.600
  • the non-bioactive fluorine compound is the non-bioactive fluorine compound
  • Photoinitiator 1 (Ebecryl P-115, SK entis),
  • Photoinitiator 2 (Borate V, Spectra group)
  • Photoinitiator 3 (irgacure 250, BASF), and
  • DBTDL dibutyltin dilaurate
  • the above prepared photo-polymeric composition was coated with 7 ratios of triacetylcell of 80 ? Eta thickness on a TAC substrate using a meyer bar and cured at 40 ° C for 30 minutes.
  • the sample was allowed to stand for at least 24 hours in a dark room under constant temperature and humidity conditions at about 25 ° C and about 50% relative humidity.
  • the hologram recording medium coated surface prepared in each of the above-described embodiment and comparative example was laminated to a slide glass, and the laser was fixed so as to pass through the glass surface in advance during recording.
  • 10 is the recording light intensity (mW / cin 2) and, PD is output quantity of the transmitted beam and the output quantity (mW / cuf) of the diffracted beam, PT is recorded a sample of the sample after recording (mW / ciif).
  • Table 1 The measurement results are summarized in Table 1 below.
  • the non-bioactive fluorinated compound prepared according to the present example was dissolved in a mixture of poly (isocyanate) and isophthalic acid It has been found that the photopolymer composition used with the maleic monomer can provide a hologram that achieves a high diffraction efficiency with a large refractive index modulation value (?) Compared to the comparative example.
  • the plasticizer component and the non-bioactive fluorine compound of the present invention are used at the same time, due to securing the flowability of the components in the polymer matrix and the movement of the non-reactive low refractive materials (non-reactive fluorine compound and plasticizer) We can clearly see that sleeping efficiency can be achieved.

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Abstract

La présente invention concerne une composition photopolymérisable, un support d'enregistrement holographique produit à partir de la composition, un élément optique comprenant le support d'enregistrement holographique, et un procédé d'enregistrement holographique utilisant la composition photopolymérisable, la composition photopolymérisable comprenant : une matrice polymère, contenant un produit de réaction d'un polyol à base d'acrylate et un composé qui comprend au moins un groupe isocyanate, ou un précurseur de celui-ci; un monomère photosensible; un composé à base de fluor non réactif représenté par une formule chimique spécifique; et un photo-initiateur.
PCT/KR2018/012194 2017-10-16 2018-10-16 Composé à base de fluor non réactif et composition photopolymérisable le comprenant Ceased WO2019078585A1 (fr)

Priority Applications (3)

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JP2020541633A JP7005100B2 (ja) 2017-10-16 2018-10-16 非反応性フッ素系化合物およびそれを含む光重合性組成物
CN201880067514.5A CN111247121B (zh) 2017-10-16 2018-10-16 非反应性氟化合物和包含其的光聚合物组合物
US16/756,072 US11292888B2 (en) 2017-10-16 2018-10-16 Non-reactive fluoro compound and photopolymer composition comprising the same

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KR10-2017-0134212 2017-10-16
KR20170134212 2017-10-16
KR10-2018-0122648 2018-10-15
KR1020180122648A KR102268129B1 (ko) 2017-10-16 2018-10-15 비반응성 불소계 화합물 및 이를 포함하는 광중합성 조성물

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451908A (en) * 1966-07-19 1969-06-24 Montedison Spa Method for preparing polyoxyperfluoromethylenic compounds
KR0127859B1 (ko) * 1985-11-08 1998-04-04 . 과플루오로폴리에테르의 제조방법
KR20030005988A (ko) * 2001-07-11 2003-01-23 주식회사 흥인화학 저분자량의 불소계 화합물의 혼합물을 담체로 사용한셀롤로스 기재의 장기 보존제
WO2003072625A1 (fr) * 2002-02-28 2003-09-04 Luvantix Co., Ltd. Composition de resine photodurcissable pour guide d'ondes optique, et guide d'ondes optique fabrique a partir de ladite composition
US20100024685A1 (en) * 2008-07-29 2010-02-04 Shin-Etsu Chemical Co., Ltd. Fluorine-containing acrylate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451908A (en) * 1966-07-19 1969-06-24 Montedison Spa Method for preparing polyoxyperfluoromethylenic compounds
KR0127859B1 (ko) * 1985-11-08 1998-04-04 . 과플루오로폴리에테르의 제조방법
KR20030005988A (ko) * 2001-07-11 2003-01-23 주식회사 흥인화학 저분자량의 불소계 화합물의 혼합물을 담체로 사용한셀롤로스 기재의 장기 보존제
WO2003072625A1 (fr) * 2002-02-28 2003-09-04 Luvantix Co., Ltd. Composition de resine photodurcissable pour guide d'ondes optique, et guide d'ondes optique fabrique a partir de ladite composition
US20100024685A1 (en) * 2008-07-29 2010-02-04 Shin-Etsu Chemical Co., Ltd. Fluorine-containing acrylate

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