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WO2019112358A1 - Composition photopolymère - Google Patents

Composition photopolymère Download PDF

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Publication number
WO2019112358A1
WO2019112358A1 PCT/KR2018/015467 KR2018015467W WO2019112358A1 WO 2019112358 A1 WO2019112358 A1 WO 2019112358A1 KR 2018015467 W KR2018015467 W KR 2018015467W WO 2019112358 A1 WO2019112358 A1 WO 2019112358A1
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WO
WIPO (PCT)
Prior art keywords
refractive index
group
recording medium
silane
hologram recording
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/015467
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English (en)
Korean (ko)
Inventor
장석훈
이현섭
김헌
권세현
장영래
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Priority claimed from KR1020180156152A external-priority patent/KR102244648B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2019554535A priority Critical patent/JP6932416B2/ja
Priority to CN201880021506.7A priority patent/CN110462734B/zh
Priority to US16/607,588 priority patent/US11226557B2/en
Priority to EP18885464.0A priority patent/EP3588499B1/fr
Publication of WO2019112358A1 publication Critical patent/WO2019112358A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • G11B7/08—Disposition or mounting of heads or light sources relatively to record carriers
    • 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

Definitions

  • the present invention relates to a photopolymer composition, a hologram recording medium, an optical element and a holographic recording method.
  • the hologram recording medium records information by changing the refractive index in the holographic recording layer in the medium through the exposure process, and reads the change in refractive index in the recorded medium to reproduce the information.
  • the optical interference pattern can be easily stored in the hologram by photopolymerization of the low-molecular monomer, the optical lens, the mirror, the deflecting mirror, the filter, the diffusing screen, , A holographic optical element having a function of a projection screen 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 photopolymer composition for hologram production comprises a polymeric binder, a monomer, and a photoinitiator, and irradiates the photosensitive film produced from such a composition with laser interference light to induce photopolymerization of the local monomer.
  • the refractive index increases at a portion where a relatively large amount of monomer exists, and at a portion where a polymer binder is relatively present, a refractive index is relatively lowered to cause a refractive index modulation, and such a refractive index modulation generates a diffraction grating.
  • the refractive index modulation value n is influenced by the thickness of the photopolymer layer and the diffraction efficiency DE, and the angular selectivity becomes wider as the thickness is known.
  • An object of the present invention is to provide a hologram recording medium which has a thin thickness, realizes a large refractive index modulation value, and has improved durability against temperature and humidity. Further, the present invention is to provide an optical element including a hologram recording medium.
  • the present invention also provides a holographic recording method comprising selectively polymerizing a photoreactive monomer contained in the hologram recording medium by a coherent laser.
  • the main relaxation temperature (Tr) at which the rate of change of the phase angle with temperature in the dynamic analysis (dynami c mechanical analysis) is the largest in the range of -80 ° C to 30 ° C, Lt; RTI ID 0.0 > 0 C < / RTI >
  • an optical element including the hologram recording medium is provided.
  • a holographic recording method which includes selectively polymerizing a photoreactive monomer contained in the hologram recording medium by a coherent laser.
  • (meth) acrylate means methacrylate or acrylate.
  • the (co) polymer refers to a homopolymer or copolymer (including random copolymers, block copolymers, and graft copolymers). .
  • a hologram is formed by exposing all Means a recording medium in which optical information is recorded in a visible range and a near ultraviolet range (300 to 800 nm), and includes, for example, an in-line (Gabor) hologram, a biaxial hologram, (Holograms), holograms of pre-ful h-apertures, holograms of white light transmission (“rainbow holograms”), Deni syuk holograms, biaxial reflection holograms, edge-l iterature holograms or holographic stereograms stereograms, and the like.
  • Gabor in-line
  • Holograms biaxial hologram
  • Holograms holograms of pre-ful h-apertures
  • holograms of white light transmission (“rainbow holograms")
  • Deni syuk holograms biaxial reflection holograms
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, n-butyl, n-napyl, 1-methylpentyl, 2- methylpentyl, N-hexyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylbutyl, But are not limited to, dimethylheptyl , 1- ethyl-propyl , 1,1-dimethyl-propyl , isohexyl , 2 -methylpentyl, 4 -methylnucyl and 5-methylnucyl.
  • the alkylene group is a divalent functional group derived from an alkane, for example, a straight chain, branched or cyclic group, and includes a methylene group, an ethylene group, a propylene group, an isobutylene group, Butylpentene, tert-butylpentene, pentylene, and naphtholene.
  • the main relaxation temperature which is the point at which the rate of change of the phase angle with temperature in the dynamic analysis (dynami c mechanical analysis) in the range of -80 ° C to 30 ° C is the largest, ion temperature, Tr)
  • 15 ° C or -15 ° C to -50 ° C can realize a large refractive index modulation value while having a thin thickness.
  • the main relaxation temperature which is the point at which the rate of change of phase mgle according to the temperature in the dynamic analysis (dynami c mechanical analysis, DMA) the mobility of the components constituting the hologram recording medium is increased even at room temperature depending on whether the temperature of the hologram recording medium is in the range of 0 ° C to -15 ° C or -15 ° C to -50 ° C So that the recording characteristics can be improved. Also, as the fluidity of the medium itself is increased, counter-di f fusions of low refractive materials are generated as opposed to the direction of diffusion of the monomer, thereby maximizing the refractive index modulation value.
  • phase angle is an angle value of tan delta calculated by G '(loss modulus) (storage elastic modulus), and dynami c mechanical analysi s) can be derived.
  • the main relaxation temperature (Tr) may be a point at which the rate of change of the phase angle with temperature in the dynamic analysis is the largest in the range of -80 ° C to 30 ° C .
  • This phase angle is measured in a DMA extension mode while giving strain to a film type hologram recording medium at a constant frequency. It is possible to calculate the retardation change value according to the temperature by measuring the loss elastic modulus and the storage elastic modulus while changing the chamber temperature around the sample in the state where the continuous deformation occurs.
  • the kinetic analysis can be performed according to a conventionally known apparatus and method. Specifically, the kinetic analysis can be carried out with a strain of 0.1%, a frequency of 1 Hz and a rate of temperature increase of 5 ° C / min ≪ / RTI >
  • the hologram recording medium of the above embodiment includes a polymer matrix or a precursor thereof; And a light-reactive monomer.
  • the polymer matrix or precursor thereof may serve as a support for the hologram recording medium and the final product made therefrom, and the photoreactive monomer may serve as a recording monomer.
  • the photoreactive monomer may be selectively polymerized on the polymer matrix to cause refractive index modulation due to a portion having a different refractive index.
  • Tr The main relaxation temperature
  • the refractive index of the polymer matrix is not particularly limited, but may be, for example, from 1.45 to 1.70, or from 1.455 to 1.60, or from 1.46 to 1.53.
  • the polymer matrix or a precursor thereof include a polymer matrix containing a (meth) acrylate-based (co) polymer in which a silane-based functional group is located in a branch chain, and a silane crosslinking agent.
  • a hologram formed from a polymer matrix comprising a (co) polymer and a silane crosslinker, or a photopolymer composition comprising the precursor thereof, has significantly improved refractive index modulation values and superior temperature and humidity durability It can be implemented.
  • silane crosslinking agent and the silane-based functional group are located in the branch chain
  • the crosslink density is optimized during the manufacture of the hologram, which ensures excellent durability against temperature and humidity compared to conventional matrices.
  • the recording property can be improved by maximizing the refractive index modulation by increasing the fluidity 1110 1 between the photoreactive monomer having a high refractive index and the component having a low refractive index.
  • a crosslinked structure mediated by a siloxane bond can be easily introduced through a sol-gel reaction between a modified (meth) acrylate-based (co) polymer containing a silane-based functional group and a silane crosslinking agent containing a terminal silane- ,
  • Such siloxane bonds can provide excellent durability against temperature and humidity.
  • the (meth) acrylate-based (co) polymer and the silane crosslinking agent in which the above-mentioned silane-based functional group is located on the branch chain in the polymer matrix may be present as separate components, and also exist in the form of a complex can do.
  • the silane-based functional group may be located in the branch chain.
  • the silane-based functional group may include a silane functional group or an alkoxysilane functional group, and preferably a trimethoxysilane group may be used as an alkoxysilane functional group.
  • the silane-based functional group may form a siloxane bond through a sol-gel reaction with the silane-based functional group contained in the silane crosslinking agent to crosslink the (meth) acrylate-based (co) polymer and the silane crosslinking agent.
  • the silane crosslinking agent may be a compound having an average of at least one silane-based functional group per molecule or a mixture thereof, and may be a compound containing at least one silane-based functional group.
  • the silane-based functional group may include a silane functional group or an alkoxysilane functional group, and preferably a triethoxysilane group may be used as an alkoxysilane functional group.
  • (Co) polymer and silane crosslinking agent can be crosslinked by forming a siloxane bond through a sol-gel reaction with a silane-based functional group contained in the (meth) acrylate-based (co) polymer.
  • the silane crosslinking agent has an equivalent equivalent of the silane-based functional group of 200 1000 g / piece. Accordingly, the cross-linking density between the (meth) acrylate-based (co) polymer and the silane cross-linking agent is optimized, and excellent durability against temperature and humidity can be secured compared to the existing matrix. In addition, through the above-mentioned optimization of the crosslink density, the recording property can be improved by maximizing the refractive index modulation by increasing the mobility between the photoreactive monomer having a high refractive index and the component having a low refractive index.
  • the equivalence of the silane-based functional groups contained in the silane crosslinking agent is excessively increased to 1000 g / mol or more, the diffraction grating interface after recording may be broken due to the reduction of the crosslinking density of the matrix, and the loose crosslinking density and the glass transition temperature
  • the monomer and plasticizer components can be eluted to the surface to generate haze. If the equivalent of the silane-based functional group contained in the silane crosslinking agent is excessively decreased to less than 200 g / g, crosslinking density becomes too high, which hinders the flowability of the monomer and the plasticizer components, .
  • the silane crosslinking agent may include a linear polyether backbone having a weight average molecular weight of 100 to 2000, or 300 to 1000, or 300 to 700, and a silane-based functional group bound to the terminal or branch chain of the main chain.
  • the linear polyether backbone having a weight average molecular weight of 100 to 2000 may include a repeating unit represented by the following formula (3).
  • n is an integer of 1 or more, or 1 to 50, or 5 to 20, or an integer of 8 to 10.
  • the silane crosslinking agent can introduce a flexible polyether polyol as a main chain to improve the fluidity of the components by controlling the glass transition temperature and crosslinking density of the matrix.
  • the bond between the silane functional group and the polyether backbone may be mediated by a urethane bond.
  • the silane-based functional group and the polyether main chain may form a mutual bond through a urethane bond, more specifically, a silicon atom contained in the silane-based functional group may be bonded directly to the nitrogen atom of the urethane bond 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • An alkylene group having 1 to 10 carbon atoms, and the functional group contained in the polyether backbone can be bonded directly to the oxygen atom of the urethane bond.
  • silane crosslinking agent is produced through a reaction between an isocyanate compound containing a silane functional group and a linear polyether polyol compound having a weight average molecular weight of 100 to 2000 Lt; / RTI >
  • the isocyanate compound is 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.
  • isocyanate compound containing the silane functional group examples include 3-isocyanatopropyltriethoxysilane.
  • the polyether polyol may be, for example, a polyaddition product of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, mixed adducts and graft products thereof, And polyether polyols and polyhydric alcohols obtained by condensation of polyhydric alcohols or mixtures thereof, amines and amino alcohols.
  • polyether polyol examples include a number average molecular weight of between 0.01 and 10, a number average molecular weight of between 200 and 18000 y / mole, preferably a functionality of 011 of from 1.8 to 4.0 and a number average molecular weight of 600 to 8000 / , Particularly preferably from 1.9 to 3.1.
  • silane crosslinking agent when the silane functional group and the polyether main chain are bonded via a urethane bond, a silane crosslinking agent can be more easily synthesized.
  • the weight average molecular weight of the silane crosslinking agent is measured in a range of 1,000 to 5,000,000 days .
  • the weight average molecular weight means the weight average molecular weight (unit: g / mol) in terms of polystyrene measured by GPC method.
  • a detector such as a known analyzer and a refractive index detector may be used, and a column for analysis may be used.
  • Temperature conditions, solvent, and f low rate include a temperature of 30 ° C, a chloroform solvent (Chloroform), and an f low rate of 1 mL / min.
  • the (meth) acrylate-based (co) polymer may include a (meth) acrylate repeating unit and a (meth) acrylate repeating unit in which the silane functional group is located in the branch chain.
  • Examples of the (meth) acrylate repeating unit in which the silane functional group is located in the branch chain include repeating units represented by the following formula (1).
  • each of 3 ⁇ 4 to 3 ⁇ 4 is independently an alkyl group having 1 to 10 carbon atoms
  • 3 ⁇ 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • 3 ⁇ 4 is an alkylene group having 1 to 10 carbon atoms.
  • each of I to 3 is independently a methyl group having a carbon number of 1, a methyl group having a carbon number of 1 or 3, and a propylene group having a carbon number of 3 / Derived unit,
  • Each of which is independently a methyl group with a carbon number of 1, a hydrogen atom with a hydrogen atom, and a propylene group with a carbon number of 3, Lt; / RTI > repeat unit.
  • Examples of the (meth) acrylate repeating unit include And a repeating unit to be displayed.
  • 3 ⁇ 4 is an alkyl group having 1 to 20 carbon atoms
  • R 7 is hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably 3 or 4 carbon atoms
  • R 7 is hydrogen
  • a repeating unit derived from butyl acrylate
  • the molar ratio of the repeating unit of Formula 2 to the repeating unit of Formula 1 may be 0.5: 1 to 14: 1. If the molar ratio of repeating units of formula (1) is excessively decreased, the cross-linking density of the matrix becomes too low to serve as a support, resulting in a decrease in recording characteristics after recording, , The crosslinking density of the matrix becomes too high and the fluidity of the respective components may be deteriorated, resulting in a decrease in the refractive index modulation value.
  • the weight average molecular weight (GPC measurement) of the (meth) acrylate-based (co) polymer is
  • the weight average molecular weight means the weight average molecular weight (unit: g / mol) in terms of polystyrene measured by GPC method.
  • a detector such as a known analyzer and a refractive index detector may be used, and a column for analysis may be used.
  • Temperature conditions, solvent, and f low rate Specific examples of the measurement conditions include a temperature of 30 ° C., a chloroform solvent (Chloroform), and an f low rate of 1 mL / min.
  • the (meth) acrylate-based (co) polymer is preferably a 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • the equivalent weight means the average molecular weight between the silane functional groups. The smaller the equivalent value, the higher the functional group density. The larger the equivalent value, the smaller the functional group density.
  • the cross-linking density between the (meth) acrylate-based (co) polymer and the silane cross-linking agent is optimized, thereby ensuring excellent durability against temperature and humidity compared to the existing matrix.
  • the recording property can be improved by maximizing the refractive index modulation by increasing the fluidity (1) between the photoreactive monomer having a high refractive index and the component having a low refractive index.
  • the crosslinking density of the matrix becomes too high to inhibit the flowability of the components, May occur. Also, if the equivalent of the silane-based functional group contained in the (meth) acrylate-based (co) polymer is excessively increased to over 2,000 / unit, the crosslinking density becomes too low to serve as a support, The refractive index modulation value can be reduced over time as the interface of the diffraction gratings collapses.
  • the silane crosslinking agent may be used in an amount of 10 to 90 parts by weight, 20 to 70 parts by weight, or 22 to 65 parts by weight based on 100 parts by weight of the (meth) acrylate-based (co) polymer. have.
  • the silane crosslinking agent content is excessively decreased with respect to 100 parts by weight of the (meth) acrylate-based (co) polymer, the curing rate of the matrix is significantly slowed to lose its function as a support, Can easily collapse, and in the reaction product,
  • the modulus (storage elastic modulus) of the reaction product may be 0.01 MPa to 5 MPa. As a specific example of the modulus measuring method,
  • a storage modulus (G ') value can be determined at a frequency of 1 Hz at room temperature (20 ° C to 25 ° C) using a DHR (di scover hybr idometer) instrument.
  • the glass transition temperature of the reaction product may be from -40 ° C to 10 ° C.
  • a 0.1% strain is measured using a DMA (dynami c mechanic cal analys) , frequency 1 Hz, heating rate
  • a method of measuring a change in the phase angle (loss modulus) of a film coated with the photopolymerizable composition in the range of -80 ° C to 30 ° C under the setting condition of 5 ° C / min.
  • the polymer matrix or its precursor is a polymer matrix comprising the reaction product of a compound containing at least one isocyanate group and a polyol.
  • the compound containing at least one isocyanate group may be a known compound having at least one NCO functional group per molecule or a mixture thereof and may be a compound containing at least one isocyanate group.
  • the compound containing at least one isocyanate group is an aliphatic , cycloaliphatic, aromatic or aromatic aliphatic mono-di-, tri- or poly-isocyanate.
  • compounds containing a group the at least one isocyanate is a urethane, urea, carbodiimide, acyl urea, isocyanurate, allophanate, biuret, oxadiazolyl Ghintec Leone and right inlet-dione or already monomer having a nook Saadi-triazine-dione Structure (Oligo- and polyisocyanates) of relatively high molecular weight of di- and / or triisocyanates.
  • the compound containing at least one isocyanate group include at least one compound selected from the group consisting of butylene diisocyanate, hexylene methylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl ) Octane, 2,2,4 - and / or 2,4,4-trimethylnucleomethylene diisocyanate, isomeric bis (4,4'-isocyanatocyclohexyl) methane and any desired isomers 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • the polyol which reacts with the compound containing at least one isocyanate group to form a polymer matrix may be an aliphatic, aromatic aliphatic or cycloaliphatic diol, triol and / or higher polyol having 2 to 20 carbon atoms.
  • diols examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl But are not limited to, glycols, 2-ethyl-2-butylpropanediol, trimethylpentanediol, diethyloctanediol positional isomers, 1,3-butylene glycol, , 2, 2-dimethyl-3-hydroxypropyl, dimethyl-3- (2-methyl- And hydroxypropionate.
  • triols examples include trimethylolethane, trimethylolpropane or glycerol.
  • Suitable highly-functional alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.
  • the polyols also include aliphatic and cycloaliphatic polyols of relatively high molecular weight such as polyester polyols, polyether polyols, polycarbonate polyols, hydroxy-functional acrylic resins, hydroxy-functionalized urethanes, hydroxy- 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- 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • Polyhydric alcohols such as dihydroxycyclo- nucleic acid, 1,4-dimethylolcyclo-nucleic acid, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or mixtures thereof, and optionally trimethyl
  • polyols such as olpropane or glycerol
  • a catalyst such as succinic acid, glutaric acid, adipic acid, pimelic acid
  • Aliphatic such as terephthalic acid, terephthalic acid, isophthalic acid, 0- phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or trimellitic acid and acid anhydrides such as 0- phthalic anhydride, trimellitic anhydride or succinic anhydride, , Linear aliphatic or aromatic di- or polycarboxylic acids or anhydr
  • di- and polyhydroxy compounds of cyclic aliphatic and / or aromatic are also suitable as polyhydric alcohols for the preparation of polyester polyols.
  • polyhydric alcohols for the preparation of polyester polyols.
  • free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides of the lower alcohols or the corresponding polycarboxylates, or mixtures thereof, in the preparation of the polyesters.
  • the polyester polyol that can be used in the synthesis of the polymer matrix is one of a lactone - are or with the copolymer, which preferably butyrolactone, £ _-caprolactone and / or methyl - £ - lactone, such as caprolactone Or lactone mixture with a suitable bifunctional and / or higher functional initiator molecule, such as the above-mentioned small molecular weight polyhydric alcohol, for example as a synthetic component for polyester polyols.
  • a lactone - are or with the copolymer, which preferably butyrolactone, £ _-caprolactone and / or methyl - £ - lactone, such as caprolactone Or lactone mixture with a suitable bifunctional and / or higher functional initiator molecule, such as the above-mentioned small molecular weight polyhydric alcohol, for example as a synthetic component for polyester polyols.
  • 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, Mixed adducts and graft products, and polyhydric alcohols or their Those obtained by alkoxylation of polyether polyols and polyhydric alcohols, amines and amino alcohols obtained by condensation of the mixture.
  • the polyether polyols include OH functionalities of 1.5 to 6 and number average molecular weights of 200 to 18000 g / mole, OH functionalities of preferably 1.8 to 4.0 and number average molecular weights of 600 to 8000 g / mole, Poly (propylene oxide) in the form of random or block copolymers, poly (ethylene oxide) and combinations thereof, having an OH functionality of 1.9 to 3.1 and a number average molecular weight of 650 to 4500 g / mol, Or poly (tetrahydrofuran) and mixtures thereof.
  • 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 a relatively large amount of polymer is present, and at a portion where a polymer binder is relatively present, the refractive index is relatively low, , And the diffraction grating is generated by such refractive index modulation.
  • examples of the photoreactive monomer include (meth) acrylate type a, p-unsaturated carboxylic acid derivatives such as (meth) acrylate,
  • the photoreactive monomer is a polyfunctional (meth) acrylate monomer having a refractive index of 1.5 or more, or 1.53 or more, or 1.5 to 1.7, and the refractive index is 1.5 or more, or 1.53 or more, or 1.5 to 1.7.
  • the functional (meth) acrylate monomers may include halogen atoms (bromine, iodine, etc.), sulfur (S), phosphorus, or aromatic rings.
  • polyfunctional (meth) acrylate monomer having a refractive index of 1.5 or more include bi sphenol A modi fi ed diacrylate series, fuorene acrylate series (HR 6022 - Miwontt), bi sphenol fuorene epoxy aery late series (HR6100, HR6060, HR6042, etc. - Miwonf soil), Halogenated epoxy acrylate series (HR1139, HR3362, etc., Miwon / tt).
  • the photoreactive monomer is a monofunctional (meth) acrylate monomer.
  • the monofunctional (meth) acrylate monomer may include an ether bond and a fluorene functional group in the molecule.
  • Specific examples of the monofunctional (meth) acrylate monomer include phenoxybenzyl
  • the photoreactive monomer may have a weight average molecular weight ranging from 50 g / mol to 1000 g / mol, or from 200 g / mol to 600 g / m.
  • the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by GPC method.
  • the hologram recording medium of the embodiment may further include a photoinitiator.
  • the photoinitiator is a compound which is activated by light or actinic radiation and initiates polymerization of a compound containing a photoreactive functional group such as the photoreactive monomer.
  • conventionally known photoinitiators may be used without any limitation, and specific examples thereof include a photo radical polymerization initiator, a photo cationic polymerization initiator, and a photoanion polymerization initiator.
  • photoradical polymerization initiator examples include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocene, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, Derivatives, and amine derivatives.
  • examples of the photocatalytic polymerization initiator include 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ', 4,4' tetrax (t-butyldimethylbenzyl) benzophenone, 3 phenyl-5-i soxazo 1, 2-mercapto benzimidazole, bi 2, 4, 5-tr ipheny 1 imidazole, (Product name: Irgacure 184 / manufacturer: BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (product name: Irgacure 651 / manufacturer: BASF) : Irgacure 369 / Manufactured by BASF), and bis (r
  • photocationic polymerization initiator examples include diazonium salts, sulfonium salts, and iodonium salts, and examples thereof include sulfonic acid esters, imidosulfuric acid esters, carbonate, di-alkyl-4-hydroxyphenyl sulfonium salts, aryl sulfonate-_ p-nitrobenzyl ester, silanol-aluminum complex, (r
  • photocationic polymerization initiator examples 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
  • Examples of the photoanion polymerization initiator include a borate salt, and examples thereof include butyrylchlorine butyl triphenyl borate (BUTYRYL CHOLINE BUTYL TRIPHENYLBORATE). More specific examples of the photoanion polymerization initiator include commercially available products such as Borate V (manufacturer: Spectra group).
  • the photopolymer composition of the above-mentioned examples may use one molecule (type I) or two molecules (type I I) initiator.
  • the (Type I) system for the free radical photopolymerization is, for example, an aromatic ketone compound combined with a tertiary amine such as benzophenone, alkylbenzophenone, 4, -bis (dimethylamino) benzophenone (Michler's ketone ), Anthrone and halogenated benzophenone or mixtures of the above types.
  • the bis (type II) initiators include benzoin and derivatives thereof, benzyl ketal, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, phenylglycine Alpha-aminoalkylacetophenone, 1- [4- (phenylthio) phenyl] octane-1,2-dione 2- (0-benzoyloxime) and alpha -Hydroxyalkylphenone, and the like.
  • acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • bisacylphosphine oxide bisacylphosphine oxide
  • phenylglycine Alpha-aminoalkylacetophenone 1- [4- (phenylthio) phenyl] octane-1,2-dione 2- (0-benzoyloxime) and alpha -H
  • the hologram recording medium of this embodiment may be a polymer matrix, 1% to 80% by weight of the precursor; 1% to 80% by weight of the photoreactive monomer; And 0.1% to 20% by weight of a photoinitiator.
  • the photopolymer 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 hologram recording medium may further include at least one selected from the group consisting of a phosphate compound and a low refractive index fluorine compound.
  • the phosphate compound and the low refractive index fluorine compound have a lower refractive index than the photoreactive monomer, thereby lowering the refractive index of the polymer matrix, thereby maximizing the refractive index modulation of the photopolymer composition.
  • the phosphate compound acts as a plasticizer to lower the glass transition temperature of the polymer matrix to increase the mobility of the photoreactive monomer and the low refractive index, and to contribute to the improvement of the moldability of the photopolymer composition have.
  • the fluorine-based compound may include at least one functional group selected from the group consisting of an ether group, an ester group and an amide group, and at least two difluoromethylene groups. More specifically, the fluorine-based compound may have a structure represented by the following formula (4) in which a functional group including an ether group is bonded to both terminals of a central functional group including a direct bond or an ether bond in two difluoromethylene periods.
  • R n and R 12 are each independently 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • Is methyl tengi difluoromethyl, and 11 ⁇ 2 mitmyo 16 is methyl tengi, each independently, a methylene group to 3 ⁇ 4 4 and each independently represents difluoromethyl, 3 ⁇ 4 7 and 8 are each independently a polyalkylene oxide group, is greater than or equal to 1, Or an integer from 1 to 10, or from 1 to 3.
  • 3 ⁇ 4 2 is methyl tengi difluoro, each independently, is 3 3 ⁇ 4 and 3 ⁇ 4 6 is methyl tengi, each independently, a 1? 14, and 15 are each independently a difluoromethylene group, and 3 ⁇ 4 7 and Each independently represents 2-methoxyethoxymethoxy group, and ??? 1 is an integer of 2.
  • the fluorine-based compound may have a refractive index of less than 1.45, or more than 1.3 and less than 1.45. As described above, since the photoreactive monomer has a refractive index of 1.5 or more, the fluorine-based compound can lower the refractive index of the polymer matrix through the refractive index lower than that of the photoreactive monomer, thereby maximizing the refractive index modulation with the monomer.
  • the content of the fluorine-based compound may be 30 parts by weight to 150 parts by weight, or 50 parts by weight to 110 parts by weight based on 100 parts by weight of the light-reactive monomer.
  • the content of the fluorine-based compound is excessively decreased with respect to 100 parts by weight of the photoreactive monomer, the refractive index modulation value after recording is lowered due to the lack of the low refractive index, and the content of the fluorine-based compound is excessively increased with respect to 100 parts by weight of the photoreactive monomer , There may arise haze due to compatibility with other components or a problem that some fluorine compounds are eluted to the surface of the coating layer.
  • the fluorine-based compound may have a weight average molecular weight of about 300 or more, or about 300 to about 1,000.
  • a specific method of measuring the weight average molecular weight is as described above.
  • phosphate compound examples include triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.
  • the phosphate-based compound together with the fluorine-based compound described above may be used in a ratio of 1: 5: 1. ≪ / RTI >
  • the phosphate compound may have a refractive index of less than 1.5 and a molecular weight of 700 or less.
  • the hologram recording medium may further include a photosensitive dye.
  • the photosensitive dye acts as an enhancer for increasing or decreasing the photoinitiator. More specifically, the photosensitive dye is stimulated by light irradiated to the photopolymer composition to serve as an initiator for initiating the polymerization of the monomer and the crosslinking monomer can do.
  • the photopolymer composition may comprise from 0.01% to 30%, or from 0.05% to 20% by weight of the photosensitive dye.
  • 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 photosensitive dye include a sulfonium derivative of ceramidonine, sul fonium der ive ive, new methylene blue, thioerythrosine triethylammonium, 6-acetylamino- Methyl ceramidonin, eosin, erythros ine, rose bengal, thionine, basic yellow, and the like.
  • An organic solvent may be used in the production of the hologram recording medium.
  • the organic solvent include ketones, alcohols, acetates and ethers, and mixtures of two or more of them.
  • organic solvent examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Methanol, ethanol, n-propanol, 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • Alcohols such as propanol, 11 -butanol, butanol, and butanol; Ethyl acetate, propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or mixtures of two or more thereof.
  • the organic solvent may be added to the photopolymer composition at the time of mixing the components contained in the photopolymer composition for producing the hologram recording medium, or may be added to the photopolymer composition while the components are dispersed or mixed in the organic solvent.
  • the photopolymer composition may comprise an organic solvent such that the concentration of the total solids of the components contained is from 1 wt% to 70 wt%, or from 2 wt% to 50 wt%.
  • the photopolymer composition may further include other additives, a catalyst, and the like.
  • the photopolymer composition may comprise a catalyst commonly known for promoting polymerization of the polymer matrix or light-reactive monomer.
  • the catalyst include tin octanoate, zinc octanoate, dibutyltin dilaurate, dimethyl bis [(1-oxoneodecyl) oxy] stannane, dimethyl tin dicarboxylate, zirconium bis I) -toluenesulfonic acid ( 1) -1 : 0 1 116116311 1 0 011 801 ( 1) or a tertiary amine such as 1,4-diazabicyclo [2.2.2] octane 1, 3-tetramethylguanidine, 1, 3, 4, 6, 7, 8-Nucleic acid hydro-1-methyl-pyrimido (1,2) Pyrimidine and the like.
  • Examples of the other additives include a defoaming agent, and the defoaming agent may be a silicone-based reactive additive.
  • Examples of the defoaming agent include 1 6 0 0 1 (1 2500). Even at thickness of 30 _ 0.020 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • the hologram recording medium may be implemented to 5 / Fe - 30 _ the diffraction efficiency of 50% or more in thickness, or less than 85%, or 85 to 99%.
  • the polymer matrix or the precursor-forming component thereof may first be uniformly mixed, and the silane crosslinking agent may be mixed with the catalyst to prepare a process for forming a hologram.
  • the photopolymer composition may be mixed with any of the components of the photopolymer composition without any limitations, such as a mixer, a stirrer, or a mixer, To 100 [deg.] (1, preferably
  • the polymer matrix or its precursor-forming component may first be homogeneously mixed and then a liquid formulation which is cured at a temperature of 20 ° C or higher.
  • the temperature of the curing may vary depending on the composition of the photopolymer and is promoted, for example, by heating to a temperature of 30 ° to 180 ° C.
  • the photopolymer may be injected into a predetermined substrate or mold or coated.
  • a method of recording a visual hologram on a hologram recording medium manufactured from the photopolymer composition can use a conventionally known method without any limitation, and adopts the method described in the holographic recording method of the embodiment to be described later as an example can do.
  • a holographic recording method may be provided, which comprises selectively polymerizing the photoreactive monomer contained in the photopolymer composition by a coherent laser.
  • a medium in a state in which no visual hologram is recorded can be manufactured, and a visual hologram can be recorded on the medium through a predetermined exposure process.
  • a visual hologram can be recorded on media provided through the process of mixing and curing the photopolymer 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 an optical lens, a mirror, a deflecting mirror, a filter, a diffusing screen, a diffraction member, a light guide, a waveguide, a holographic optical element having a function of 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 the 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 pre-inputs three-dimensional image information of an object to be recorded on the display unit.
  • the input unit may be provided with an electric driving liquid crystal SLM (electric addressed lid crystal SLM) Three-dimensional information of an object can be input, and an input beam can be used at this time.
  • the optical system may include a mirror, a polarizer, a beam splitter, a beam shutter, a lens, and the like.
  • the optical system includes an input beam for transmitting a laser beam emitted from a light source unit to an input unit, a recording beam for sending to a display unit, The beam can be distributed by the beam.
  • the display unit receives the three-dimensional image information of the object from the input unit and transmits the three-dimensional image information to the hologram plate made of an optically driven SLM 2019/112358 1 »(: 1 ⁇ 1 ⁇ 2018/015467
  • the three-dimensional image information of the object can be recorded through the interference of 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 for inputting the 3D image and a position for reproducing the 3D image.
  • a hologram recording medium having a thin thickness, a large refractive index modulation value and improved durability against temperature and humidity, an optical element including the same, and a holographic recording method using the hologram recording medium.
  • the polyol, photoreactive monomer high refractive index acrylate, refractive index 1.600, HR6022 [Miwon]
  • safranin 0 die, manufactured by Sigma Aldrich
  • non-reactive low refractive material of Production Example 2 tributyl phosphate (ibid), Irgacure 250 (BASF), and methyl isobutyl ketone (MIBK) were added to the reaction mixture. And the mixture was stirred with a Paste mixer for about 10 minutes to obtain a clear coating solution.
  • MFA-75X (Asahi Kasei, hexafunctional isocyanate, diluted to 75 wt% in xylene) was added, and the mixture was further stirred for 5 to 10 minutes.
  • DBTDLCdibutyl tin diurate as a catalyst was added thereto and stirred for about 1 minute Using a Meyer bar, 80 / M thick
  • the silane crosslinking agent of Preparation Example 4 was added to the coating solution and further stirred for 5 to 10 minutes. Then, the catalyst DBTDL was added to the coating solution, After stirring, the coating was coated on a TAC substrate of 80 / M in thickness by using a meyer bar and dried at 40 ° C for 1 hour.
  • the temperature was set to -80 ° C to 30 ° C with the use of a DMA (dynami c mechani cal analys) equipment with a strain of 0.1%, a frequency of 1 Hz and a heating rate of 5 ° C / min.
  • DMA dynami c mechani cal analys
  • the phase angle is the angular value of tan del ta calculated by G "(loss modulus) / G '(strorage modulus), and the larger the phase angle value, the higher the vi scous characteristic of the material do.
  • the point at which the rate of change of the phase angle with temperature was largest was defined as the main relaxation temperature and the Tr value of the hologram recording medium obtained in the examples and the comparative examples was confirmed.
  • a holographic recording was made through interference of two interfering lights (reference light and object light), and the transmissive recording made the two beams incident on the same side of the sample.
  • the diffraction efficiency is changed according to the incident angle of the two beams, and when the incident angles of the two beams are the same, the beam becomes non-santed.
  • the non-slanted recording is generated perpendicular to the film, since the incident angles of the two beams are normalized.
  • the refractive index modulation value (An) can be calculated from the general formula (2).
  • 1 is the thickness of the photopolymer layer, 1 is a refractive index modulation value,? Is a diffraction efficiency, and ⁇ is a recording wavelength.
  • Non-reactive plasticizer Tributyl phosphate (Molecular Weight 266.31, refractive index 1.424, purchased from Sigma-Aldrich) As shown in Table 1 above, a dynamic mechanical analysis in the region of -80 ° C to 30 ° C The main relaxation temperature (Tr), which is the point where the rate of change of the phase angle with temperature is largest,
  • the hologram recording media of Examples 1 to 4 having a temperature of 0 ° C or less can realize a refractive index modulation value (An) of 0.024 or more.
  • the hologram recording medium of Comparative Example 1 in which the Tr was 13 ° C had a relatively low diffraction efficiency as compared with the Example.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Holo Graphy (AREA)

Abstract

La présente invention concerne : un support d'enregistrement d'hologramme présentant une température de relaxation principale de 0 °C ou moins telle que déterminée par une analyse mécanique dynamique dans la plage de - 80°C à 30°C, la température de relaxation principale étant le point auquel la vitesse de changement induite par la température de l'angle de phase est le plus grande ; un élément optique comprenant le support d'enregistrement d'hologramme ; et un procédé d'enregistrement holographique comprenant une étape de polymérisation sélective de monomères à sensibilité optique contenus dans le support d'enregistrement d'hologramme au moyen d'un laser cohérent.
PCT/KR2018/015467 2017-12-08 2018-12-07 Composition photopolymère Ceased WO2019112358A1 (fr)

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JP2019554535A JP6932416B2 (ja) 2017-12-08 2018-12-07 フォトポリマー組成物
CN201880021506.7A CN110462734B (zh) 2017-12-08 2018-12-07 全息图记录介质、光学元件以及全息记录方法
US16/607,588 US11226557B2 (en) 2017-12-08 2018-12-07 Photopolymer composition
EP18885464.0A EP3588499B1 (fr) 2017-12-08 2018-12-07 Composition photopolymère

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US20210239894A1 (en) * 2018-09-27 2021-08-05 Lg Chem, Ltd. Hologram medium
EP3779595A4 (fr) * 2018-09-27 2021-10-13 Lg Chem, Ltd. Support d'hologramme
US11994704B2 (en) 2018-09-27 2024-05-28 Lg Chem, Ltd. Hologram medium

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