WO2019078585A1 - Non-reactive fluorine-based compound and photopolymerizable composition including same - Google Patents

Abstract

The present invention relates to a photopolymerizable composition, a holographic recording medium produced from the composition, an optical element including the holographic recording medium, and a holographic recording method using the photopolymerizable composition, wherein the photopolymerizable composition includes: a polymer matrix, including a reaction product of an acrylate-based polyol and a compound that includes at least one isocyanate group, or a precursor thereof; a photosensitive monomer; a non-reactive fluorine-based compound represented by a specific chemical formula; and a photoinitiator.

Description

 Title of the Invention

 Non-pro-inflammatory fluorinated compounds and photopolymerizable compositions containing them

TECHNICAL FIELD

 Related application (mutual quotation with field

 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. BACKGROUND ART [0002]

 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.

 Since 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.

 Typically, 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.

In the photopolymerization process, 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. In recent years, 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.

DETAILED DESCRIPTION OF THE INVENTION

 [Technical Problem]

 The present invention aims to provide a non-reactive fluorinated compound having a specific chemical structure.

 Also, there is a need to provide a photopolymerizable composition containing the non-bio-reactive fluorinated compound, which can provide photopolymerizable dyes having a thin thickness and a large refractive index modulation value more easily.

 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.

[Technical Solution]

 The present invention provides a non-bioactive fluorinated compound represented by the following general formula (1) or (2).

 A non-reactive fluorine-based compound represented by the following formula (1) or (2):

 [Chemical Formula 1]

 (2)

R ^ iC ^ R ^ OC ^ R ^^ - X-iC ^ R ^ OC ^ R ^ na-R 2 In the above 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.

 In addition,

 A)

 i) an acrylate-based polyol having an OH equivalent of 10,000 g / mol or more and a weight average molecular weight of 500,000 or more; And

 ii) an isocyanate compound;

 Polymer matrix or precursor thereof;

 B) the above-described non-bio-reactive fluorine compound;

 C) a photoreactive monomer; And

 D) a photoinitiator. In addition,

And a hologram recording layer formed by the photopolymerizable composition. 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. In the present specification, (meth) acrylate is used as a concept including both methacrylate and acrylate.

 In this specification, 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. Hereinafter, the present invention will be described in detail. First, according to one aspect of the present invention, there is provided a non-bioactive fluorine compound represented by the following general formula (1) or (2).

 A non-reactive fluorine-based compound represented by the following formula (1) or (2):

 [Chemical Formula 1]

 (2)

R '- (CR ³ R ⁴ -O-CR ⁵ R ⁶ ) n ₂ -X- (CR ³ R ⁴ -O-CR ⁵ R ⁶ ) n ₃ -R ²

 In the above 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, and 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, and black is alkylene group having 1 to 10 carbon atoms.

 In the present specification, the term "non-bioactive" as used herein means that the compound is not compatible with an acrylate-based polyol, an isocyanate, and a photopolymerizable monomer.

 In this specification, the 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. In the above formulas, 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

Lt; RTI ID = 0.0 > 3. ≪ / RTI >

 (3)

- (CF ₂ -O-CF ₂ ) - 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. At this time, 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. Specifically, when an ester group is introduced into a terminal blocking group, an acyl chloride compound and trimethylamine can be bonded using a base. When an ether group is introduced into a terminal blocking group, an alkoxy chloride compound and NaH are used to form a fluorine Lt; RTI ID = 0.0 > ethylene glycol < / RTI > Further, according to an embodiment of the invention,

 A)

 i) an acrylate-based polyol having an OH equivalent of 1000 g / mol or more and a weight average molecular weight of 500,000 or more; And

 ii) an isocyanate compound;

 Polymer matrix or precursor thereof;

 B) the above-described non-bio-reactive fluorine compound;

 C) a photoreactive monomer; And

D) 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 In addition, in the case of using 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, In the hologram formed from the composition, the refractive index can serve as a portion having a different refractive index to enhance the refraction.

 As described above, the polymer matrix may include a copolymerization product between an acrylate-based polyol and a compound containing at least one isocyanate group. Accordingly, 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. As described above, it is preferable to use an acrylate-based polyol having an OH equivalent of 1000 g / mol or more and a weight-average molecular weight of 500,000 or more, as the polyisocyanate-antifouling component.

 Among them, 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.

 Examples of the alkyl acrylate component having 1 to 5 carbon atoms in the alkyl group as the monomer for constituting the above acrylate repeating unit include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, and pentyl (meth) acrylate.

 Examples of the hydroxyalkyl acrylate monomer having 1 to 5 carbon atoms in the alkyl group 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.

 More specifically, 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.

Specific examples of 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 diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate and / or triphenylmethane 4,4 ', 4 "-triisocyanate Can The.

 On the other hand, 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.

According to one embodiment of the present invention, in view of the matrix crosslinking control of the polyol component and the isocyanate component, the isocyanate compound 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.

 Examples of the diols 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.

 Examples of the triols 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.

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- The use of higher functional polyols, such as glycine, in combination with other polyols such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid Terephthalic acid, isophthalic acid, 0-phthalic acid, Aliphatic, cycloaliphatic, or aromatic di- or polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid or trimellitic acid, and acid anhydrides such as 0-phthalic anhydride, trimellitic anhydride or succinic anhydride, Is a linear polyester diol, such as can be prepared in known manner from an acid or an anhydride thereof. Of course, di- and polyhydroxy compounds of cyclic aliphatic and / or aromatic are also suitable as polyhydric alcohols for the preparation of polyester polyols. Instead of 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.

 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 For example, those prepared by reaction of pentanediol with 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.

Specific examples of 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. On the other hand, the photopolymerizable composition includes a non-reactive fluorinated compound represented by the following general formula (1) or (2).

 A non-bioactive fluorine-based compound represented by the following formula (1) or (2):

 [Chemical Formula 1]

 (2)

R @ ^{2 is a group of} formula --NR @ ² R @ ^2,

 In the above formula (1) or (2)

R1 and R2, 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.

 In the case of using the non-bioactive fluorine compound, by maximizing the difference in refractive index between the exposed portion and the non-exposed portion, the sensitivity to recording light can be increased, and thus the recording efficiency can be remarkably increased.

As described above, 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

1.30 to L40. In this case, it is possible to maximize the difference in refraction between the optically maleic monomer, that is, the recording monomer which records information by exposure, and thus the exposure sensitivity can be remarkably increased.

Further, 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. On the other hand, the photoreactive monomer may include a polyfunctional (meth) acrylate monomer or a monofunctional (meth) acrylate monomer.

 As described above, in the photopolymerizable composition of the photopolymerizable composition, 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.

 (Meth) acrylate, (meth) acrylate, (meth) acrylonitrile, or (meth) acrylonitrile. Methacrylic acid, or a compound containing a vinyl group or a thiol group.

 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社), 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. Specific examples of the monofunctional (meth) acrylate monomer include phenoxybenzyl (meth) acrylate, (meth) acrylate, benzyl (meth) acrylate, 2- (phenylcyano) ethyl (meth) acrylate, or biphenylmethyl (meth) acrylate.

 On the other hand, 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. Meanwhile, 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.

 As the 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. .

 Specific examples of the photoradical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, And derivatives thereof. More specifically, 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 BASF).

Examples of the cationic ion-generating initiator include diazonium salts, sulfonium salts, and iodonium salts, and examples thereof include sulfonic acid esters, imidosulfonates, dialkyl- (Η6-benzene) (η5-cyclopentadienyl) iron (Π), 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.

 In addition, 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. Examples of the bis (type Π) initiator 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.

 The photopolymerizable composition comprises A) a polymer matrix or precursor thereof

20 to about 80 weight _^0/0, B) non-reactive fluorine-containing compound from about 5 to about 40 parts by weight _^0/0; C) The male flare monomer about 10 to about 70 weight _^0/0; ., And D) 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. As described later, 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). According to an embodiment of the present invention, 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 Ν, 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.

When such a plasticizer is used together with the above-mentioned non-reactive blend-based compound, its effect can be maximized. Specifically, 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- . On the other hand, 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 a combination of two or more thereof.

 The photopolymerizable composition may further include an organic solvent. Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, and mixtures of two or more thereof.

 Specific examples of 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.

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

By weight to 50% by weight.

The photopolymerizable composition may further include other additives, a catalyst, and the like. For example, the photopolymerizable composition may comprise a catalyst commonly known for promoting polymerization of the polymer matrix or the photo-labile monomer. Examples of 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. On the other hand, according to another embodiment of the present invention, a hologram recording medium including a hologram recording layer made from a photopolymerizable composition can be provided.

 As described above, 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 photopolymerizable composition of this embodiment is prepared by uniformly mixing each component contained therein and drying and curing the composition at a temperature of 20 or more. Thereafter, the photopolymerizable composition of the present invention is exposed to a visible range and a near ultraviolet region (300 to 800 nm) Lt; RTI ID = 0.0 > hologram < / RTI >

 In the photopolymerizable composition of this embodiment, 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.

 Meanwhile, in the photopolymerizable composition of one embodiment, 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 temperature of the cure will vary depending on the ^composition, the photopolymerization Castle, for example 30 to 180 ^° C, preferably from 40 to 120 ^° C, particularly preferably 50 To < RTI ID = 0.0 &^gt; 100 C. < / RTI >

 During the curing, the photopolymerization may be injected into a predetermined substrate or mold or coated.

 Meanwhile, 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 . According to another embodiment of the present invention, there is provided 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. As described above, it is possible to manufacture a medium in which the visual hologram is not recorded through the process of shaking and curing the photopolymerizable composition, and the 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 shaking and curing the photopolymerizable composition, using known devices and methods under commonly known conditions. On the other hand, according to another embodiment of the invention, an optical element including a hologram recording medium can be provided.

 Specific examples of 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. In addition, The input unit is a part for preliminarily inputting three-dimensional image information of an object to be recorded on the display unit. For example, 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. At this time, 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. On the other hand, 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. 【Effects of the Invention】

 According to the present invention, there is provided 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. DETAILED DESCRIPTION OF THE INVENTION

 Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

<Conduct ^!> Preparation of non-bioactive fluorinated compound 1

In a 1000 ml flask add 20.51 g of 2,2 - ((oxybis (1,1,2,2-tetrafluoroethane-2,1-diyl) bis (oxy)) bis (2,2-difluoroethan-1 -ol) after standard, it was dissolved in 500g of tetrahydrofuran, while stirring at ^{0 ° C sodium hydride (6 0} % dispersion in mineral oil) 4. ⁴⁰ g was carefully added several times.

 After stirring at 0 ° C for 20 minutes, 12.50 ml of 2-methoxyethoxymethyl chloride was slowly dropped. It was confirmed by using 1 H NMR that all of the water was consumed, and the reaction solution was decompressed to remove all the unreacted solvent.

 The organic layer was collected three times with 300 g of sodium chloride, filtered through magnesium sulfate, and then dichloromethane was removed by reduced pressure to obtain 29 g of a liquid product having a purity of 95% or more at a yield of 98%.

 The 589 nm refraction of the liquid product was measured to be 1.37 using an Abbe refractometer.

The formula of the product is as follows.

Preparation of non-bioactive fluorinated compound 2

A ((oxybis (l, l, 2,2-tetrafluoroethane-2, l- diyl)) bis (oxy)) bis (2,2-difluoroethan- 1 -ol) 12.30g - a 1,000 ml flask, 2, ^{2 '} , Diluted in 300 ml of tetrahydrofuran, and 16.77 ml of hexanoyl chloride is added dropwise at 0 ° C with stirring.

 After 20 minutes, 16.74 ml of triethylamine is added dropwise, the ice-bath is removed, the temperature is gradually raised to room temperature, and the reaction is allowed to proceed until the reaction is confirmed by TLC.

After the reaction is completed, the triethylamine hydrochloride salt generated as a byproduct is removed by filtration, the solvent THF is removed by decompression, and then extracted three times with dichloromethane and 1N aqueous NaOH solution. 20 deployed subjected to column chromatography in a liquid condition, purity ^90%, or more of the product: After that, Ethyl acetate: n-haxane = 1 . Using the Abbe refractometer,

The result was measured as L38.

Acrylate-based Polyol Component and Preparation

34.5 g of methyl acrylate, 57.5 g of butyl acrylate, and 8 g of 4-hydroxybutyl acrylate were added to a 2 L jacket, and the mixture was diluted with 150 g of ethyl acetate. The reaction temperature was adjusted ^at 60 to 70 ^° C and stirring was continued for about 1 hour.

Here, into an additional n- dodecyl mercaptan 0.035g, it was carried out for 30 minutes ^more, stirred.

 Thereafter, 0.04 g of azo-bis-isobutyrylnitrile (AIBN) was added as a polymerization initiator, polymerization was continued for 4 hours or more at the reaction temperature, and the residual acrylate content was maintained until the residual acrylate content became less than 1% An acrylate-based polyurethane having a molecular weight of about 700,000 and an OH equivalent of 1802 g / OH mole was prepared. Preparation of a Photosynthetic Polymer Composition

 Each component of the composition is as summarized in Table 1 below.

 The acrylate-based polyol,

 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,

 Dye (safranin O, Sigma Aldrich)

 Photoinitiator 1 (Ebecryl P-115, SK entis),

 Photoinitiator 2 (Borate V, Spectra group)

 Photoinitiator 3 (irgacure 250, BASF), and

 After the solvent (methyl isobutyl ketone) was mixed,

Respectively, Followed by stirring with a paste mixer for about 10 minutes to prepare a transparent coating liquid. To this, a hexafunctional isocyanate component (MFA-75X, Asahi Kasei, diluted to 75% by weight in xylene) was added, and stirring was further continued for 5 minutes.

 0.01 1 g of dibutyltin dilaurate (DBTDL) as a catalyst was added, and the reaction was allowed to proceed for about 1 minute to prepare a photoreactive polymer composition. Manufacture of holographic recording media

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.

[Experimental Example: Hologram Recording]

 (1) 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.

 (2) Hologram is recorded through interference of two interfering lights (reference light and object light), and transmission type recording enters two beams on the same side of the sample. The diffraction efficiencies change with the incidence angles of the two bands, and non-slanted when the incidence angles of the two bands are the same. The non-slanted recording is generated perpendicular to the film, since the incident angles of the two beams are normalized.

 The diffraction efficiency (η) was calculated from the following general formula (1) by recording in transmission type non-slanting manner (2Θ = 45 °) using a laser of 532 nm wavelength.

 [Formula 1]

P _D + P _T

In the above general formula (1),? Is the diffraction efficiency, PD is the diffracted output power (mW / crf) of the sample after recording, and POT is the output power (mW / cuf) of the transmitted beam of the recorded sample. The laser loss (I _loss ) of the transmission type hologram is calculated from the following general formula 2 .

 [Formula 2]

In the formula 2, 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). The measurement results are summarized in Table 1 below. (Unit g)

 [Table 11

Ketone

 Modulation of refraction

 0.026 0.03 0.025 0.024 0.02 0.017 0.013 0.008 Value n

 As shown in Table 1 above, 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.

 Particularly, when 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.

Claims

Claims 1. A non-reactive fluorine-containing compound represented by the following general formula (1) or (2):

 [Chemical Formula 1]

R @ 6a --C @ ⁶ R @ ⁶ OC @ - R @

( ² )

R &lt; ² &gt; is R &lt; ^{2 &gt;}

 In the above 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 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,

 nl to &lt; RTI ID = 0.0 &gt; Ill &lt; / RTI &gt; is a repeating number of repeating units,

X is alkylene having 1 to 10 carbon atoms, and black is alkylene group having 1 to 10 carbon atoms. [Claim 2]

 In the above,

 Refractive index of less than 1.45.

[Claim 3]

 The method according to claim 1,

 A non-reactive fluorinated compound having a molecular weight of 300 or more.

Claim 4

 In Item 1,

R3 to R6 are each independently selected from the group consisting of hydrogen, A halogen atom, or an alkyl group having from ₅ to ₅ carbon atoms,

 Wherein at least half of the fluorine atom is a fluorine atom.

[Claim 5]

 The method according to claim 1,

 A non-bioactive fluorine-based compound comprising a repeating unit represented by the following formula (3):

 (3)

_{- (CF 2 -0-CF 2} ) -

[Claim 6]

 A)

 i) an acrylate-based polyol having an OH equivalent of 1000 g / mol or more and a weight average molecular weight of 500,000 or more; And

 ii) the isocyanate compound comprises a counterion;

 Polymer matrix or precursor thereof;

 B) The non-bio-compatible fluorinated compound of claim 1;

 C) Optically male. Monomer; And

 D) a photoinitiator.

7.

 The method according to claim 6,

 The acrylate-based polyol is an alkyl acrylate having 1 to 5 carbon atoms in the alkyl group; And

 Is a compound comprising a repeating unit derived from a hydroxyalkyl acrylate having 1 to 5 carbon atoms in the alkyl group.

[8]

 The method according to claim 6,

The acrylate- OH equivalent of 1000 to 2000 g / nu) and a weight average molecular weight of 600,000 to 800,000.

[Claim ^'9;

 The method according to claim 6,

 Wherein the photo-polymeric monomer comprises a polyfunctional (meth) acrylate monomer or a monofunctional (meth) acrylate monomer.

[Claim 10]

 The method according to claim 6,

 The isocyanate compound may be an aliphatic, cycloaliphatic, aromatic or aromatic aliphatic mono-isocyanate di-isocyanate, tri-isocyanate or poly-isocyanate; or

 Diisocyanate or triisocyanate oligoisocyanate having urethane, urea, carbodiimide, acyl urea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazine dione structure, or Poly-isocyanate. &Lt; / RTI &gt;

Claim 111

 The method according to claim 6,

 As the polyol component, in addition to the acrylate-based polyol,

 Aliphatic aromatic diols, triols or polyols having 2 to 20 carbon atoms;

Alicyclic diols having from 4 to 30 carbon atoms, triols or polyols; And

 An aromatic diol having 6 to 30 carbon atoms, a trio or a polyol.

Claim 12

 The method according to claim 6,

A) the polymer matrix or precursor thereof increased from 20 to 80 ^_0/0

B) non-reflective male fluorinated compound of 5 to 40 parts by weight _^0/0; C) 10 to 70% by weight of the photo-polymeric monomer; and

D) photoinitiator, 0.1 to 10 parts by weight containing _^0/0, the photopolymerizable composition.

Claims. 13]

 The method according to claim 6,

 A photopolymerizable composition, further comprising a plasticizer.

14.

 A hologram recording medium comprising a hologram recording layer formed by the photopolymerizable composition of claim 16.

15.

 An optical element comprising the hologram recording medium of claim 14. Claim 16

 14. A method of recording a hologram, comprising irradiating actinic radiation onto the hologram recording medium of claim 14 to selectively polymerize the optically maleic monomer.