WO2020050321A1 - Volume hologram-recording material composition containing triazine ring-containing hyperbranched polymer - Google Patents

Volume hologram-recording material composition containing triazine ring-containing hyperbranched polymer Download PDF

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WO2020050321A1
WO2020050321A1 PCT/JP2019/034803 JP2019034803W WO2020050321A1 WO 2020050321 A1 WO2020050321 A1 WO 2020050321A1 JP 2019034803 W JP2019034803 W JP 2019034803W WO 2020050321 A1 WO2020050321 A1 WO 2020050321A1
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hologram recording
volume hologram
composition
acrylate
meth
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PCT/JP2019/034803
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French (fr)
Japanese (ja)
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康生 富田
寿郎 大島
啓祐 大土井
督 大津
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国立大学法人電気通信大学
日産化学株式会社
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Priority to JP2020541270A priority Critical patent/JPWO2020050321A1/en
Publication of WO2020050321A1 publication Critical patent/WO2020050321A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms

Definitions

  • the present invention provides a composition for a volume hologram recording material capable of forming a pattern in which each component in the composition is moved by pattern exposure, and a spatial distribution of each component is changed, and a pattern using the composition. It relates to a forming method.
  • the present invention also relates to a volume hologram recording layer containing the hologram recording material composition and a volume hologram recording medium provided with the recording layer.
  • a holographic diffraction grating is a pattern in which a light / dark (interference) pattern of light is recorded as a pattern of a refractive index or an absorptance on a photosensitive material or the like.
  • Numerous applications have been reported in a wide range of fields such as photonics and information displays, such as band wavelength filters, photonic crystals, optical waveguide couplers, optical interconnections, stereoscopic image displays, head-up displays, and the like. In these application fields, a large change in the refractive index and a high recording sensitivity are usually required.
  • a dichromated gelatin photosensitive material or a bleached silver salt photosensitive material has been used. These have a high diffraction efficiency, but have a drawback that the processing at the time of forming the hologram is complicated and particularly requires wet development processing.
  • the Omnidex series of DuPont is widely known. This material records a hologram using a radical polymerization monomer, a binder polymer, a photoradical polymerization initiator, and a sensitizing dye as main components and utilizing a difference in refractive index between the radical polymerization monomer and the binder polymer.
  • Patent Document 1 a material system using both radical polymerization and cationic polymerization (see Patent Document 1) and a material system using cationic polymerization (see Patent Document 2) have been reported. Since they are not compatible, the hologram recording film formed of this material system has a problem that transparency is reduced due to phase separation, and scattering loss is increased due to this. Furthermore, the mechanical strength and environmental stability are still insufficient.
  • Patent Document 3 a material system using an inorganic substance network and a photopolymerizable monomer in combination has been disclosed (see Patent Document 3).
  • an inorganic material capable of forming a network is used as a binder, there is an advantage that heat resistance, environmental friendliness, and mechanical strength are excellent, and a large difference in refractive index from a photopolymerizable organic monomer can be obtained.
  • the hologram recording film formed by the system is rather brittle and has problems such as poor flexibility, processability, and coating suitability, and poor compatibility between the inorganic binder and the organic monomer to prepare a uniform coating material. There is a problem of difficulty.
  • a material in which ultrafine metal particles are dispersed in a solid matrix is disclosed as a hologram recording material (see Patent Document 4).
  • Patent Document 4 a material in which ultrafine metal particles are dispersed in a solid matrix.
  • fluidity it is necessary to impart fluidity to the matrix, and not only poor solidity, but also poor adhesion between the metal particle interface and the solid matrix, brittleness, and problems such as intrusion of water into the interface. is there.
  • Patent Document 5 a hologram recording material using an organic-inorganic hybrid polymer and organometallic fine particles having a photopolymerization-reactive group has been disclosed (see Patent Document 5).
  • heating and ultraviolet polymerization are required to fix the interference fringes, and there is a problem as an industrial process.
  • Patent Literature 6 a hologram recording material in which inorganic fine particles are dispersed in a photopolymerizable monomer is disclosed (see Patent Literature 6, Patent Literature 7, and Non-Patent Literature 1). Further, a low-shrink hologram recording material is disclosed by dispersing fine particles in a mixture of an ene compound having an ethylenically unsaturated group and a thiol compound having a mercapto group (Patent Document 8). Further, a composition for a volume hologram recording material containing a triazine ring-containing hyperbranched polymer is disclosed (Patent Document 9). However, even with these materials, there is a problem that sufficient diffraction efficiency is not obtained.
  • the present invention relates to a volume hologram recording material, wherein a triazine ring-containing hyperbranched polymer having low cohesiveness and an extremely high refractive index is used as fine particles, and (meth) acrylic is used as a component capable of dispersing and dissolving the hyperbranched polymer.
  • a composition for a volume hologram recording material capable of permanently forming a hologram having a very low light scattering loss and a high diffraction efficiency by blending a hydroxyalkyl acid with other polymerizable components, and hologram recording using the composition The purpose is to provide a medium.
  • a composition for a volume hologram recording material used for forming a pattern by pattern exposure (A) hydroxyalkyl (meth) acrylate, (B) a polymerizable compound different from the component (a),
  • the present invention relates to a composition for a volume hologram recording material, comprising (c) a triazine ring-containing hyperbranched polymer and (d) a photopolymerization initiator.
  • the ratio of the component (c) to the total volume of the component (a), the component (b), and the component (c) is 3% by volume or more and 50% by volume or less.
  • the present invention relates to a composition for a volume hologram recording material according to one aspect.
  • the present invention relates to the composition for a volume hologram recording material according to the first aspect or the second aspect, wherein the pattern exposure is interference exposure, and is used for forming a hologram by the interference exposure.
  • the polymerizable compound different from the components (b) and (a) is a polyfunctional (meth) acrylate. Composition.
  • the present invention relates to a volume hologram recording layer including the composition for a volume hologram recording material according to any one of the first to fourth aspects.
  • the present invention relates to a volume hologram recording medium including the volume hologram recording layer according to the fifth aspect.
  • the present invention relates to the volume hologram recording medium according to the sixth aspect, wherein the volume hologram recording layer has a structure in which each of the volume hologram recording layers has a plane and is disposed between two transparent substrates facing each other.
  • a step of applying the composition for a volume hologram recording material according to any one of the first to fourth aspects to a support to form a coating film, and pattern-exposing the coating film relates to a pattern forming method including a step.
  • the present invention relates to the pattern forming method according to the eighth aspect, wherein the pattern exposure is interference exposure.
  • a composition for a volume hologram recording material and a volume hologram recording medium capable of permanently forming a hologram having low light scattering loss and high diffraction efficiency.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of HB-TmDA obtained in Production Example 1.
  • FIG. 2 shows the volume hologram recording device (recording / reproducing wavelength 532 nm) used in the example.
  • FIG. 3 shows the refractive index modulation with respect to the exposure time (sec) obtained using the volume hologram recording medium of Example 1 (component (a): 4HBA, volume fraction of HB-TmDA: 19.6% by volume). It is a figure which shows the change of quantity (DELTA) n.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of HB-TmDA obtained in Production Example 1.
  • FIG. 2 shows the volume hologram recording device (recording / reproducing wavelength 532 nm) used in the example.
  • FIG. 3 shows the refractive index modulation with respect to the exposure time (sec) obtained using the volume hologram recording medium of Example 1 (component (a): 4HBA, volume fraction of HB-Tm
  • FIG. 4 shows the refractive index modulation with respect to the exposure time (sec) obtained using the volume hologram recording medium of Comparative Example 1 (component (a): THFA + NVP, volume fraction of HB-TmDA: 19.9% by volume). It is a figure which shows the change of quantity (DELTA) n.
  • FIG. 5 is a diagram showing a change in the refractive index modulation amount ⁇ n with respect to the exposure time (second), obtained by using the volume hologram recording medium of Example 2 (volume fraction of HB-TmDA: 15.1% by volume). It is.
  • FIG. 5 is a diagram showing a change in the refractive index modulation amount ⁇ n with respect to the exposure time (second), obtained by using the volume hologram recording medium of Example 2 (volume fraction of HB-TmDA: 15.1% by volume). It is.
  • FIG. 6 is a diagram showing a change in the refractive index modulation amount ⁇ n with respect to the exposure time (second), obtained using the volume hologram recording medium of Example 3 (volume fraction of HB-TmDA: 20.0 vol%). It is.
  • FIG. 7 is a diagram showing a change in the refractive index modulation amount ⁇ n with respect to the exposure time (second), obtained using the volume hologram recording medium of Example 4 (volume fraction of HB-TmDA: 23.0% by volume). It is.
  • FIG. 8 is a diagram showing a change in the refractive index modulation amount ⁇ n with respect to the exposure time (second) obtained using the volume hologram recording medium of Example 5 (volume fraction of HB-TmDA: 25.0% by volume). It is.
  • FIG. 9 shows a volume hologram recording device (recording / reproducing wavelength: 640 nm) used in the example.
  • FIG. 10 is a diagram showing a change in the refractive index modulation amount ⁇ n with respect to the exposure time (second) obtained using the volume hologram recording medium of Example 6 (volume fraction of HB-TmDA: 20.1% by volume). It is.
  • the composition for a volume hologram recording material of the present invention comprises (a) hydroxyalkyl (meth) acrylate, (b) a polymerizable compound different from the component (a), (c) a triazine ring-containing hyperbranched polymer, and (d) It is configured to include a photopolymerization initiator.
  • the (a) hydroxyalkyl (meth) acrylate in the present invention can disperse the (c) triazine ring-containing hyperbranched polymer described below, and can be used as a polymerizable compound different from the (b) (a) component described later. On the other hand, it functions as a component that can be dispersed together with the component (c).
  • (meth) acrylic acid represents both methacrylic acid and acrylic acid.
  • the component (a) is not particularly limited as long as it is a compound in which the alkyl group of the (meth) acrylic acid alkyl ester compound is substituted with at least one hydroxy group, and the alkyl group has two or more hydroxy groups. Or a compound further substituted with another substituent.
  • a hydroxyalkyl (meth) acrylate in which the alkyl group has no substituent other than the hydroxy group (the alkyl group is substituted only by the hydroxy group) can be preferably used.
  • Monohydroxyalkyl (meth) acrylates substituted with only one hydroxy group can be used.
  • Examples of the component (a) include (meth) acrylate compounds having a hydroxyalkyl group having 1 to 20 carbon atoms.
  • Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group , Hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl and hydroxyeico And a sil group.
  • These hydroxyalkyl groups may
  • component (a) examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-1 (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1-methylethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable.
  • 4-Hydroxybutyl acrylate is more preferred.
  • the compounding amount of (a) hydroxyalkyl (meth) acrylate is 0.1 to 1, based on 1 part by mass of a polymerizable compound different from the component (b) and (a). 000 parts by mass, preferably 0.5 to 500 parts by mass, more preferably 1 to 500 parts by mass, for example 1 to 100 parts by mass.
  • the polymerizable compound of the component (b) in the present invention is a compound having one or more, preferably 1 to 6 polymerizable sites in the molecule, which is polymerized by the action of a photopolymerization initiator. : There is no particular limitation as long as it is a compound different from hydroxyalkyl (meth) acrylate.
  • the polymerizable site include an ethylenically unsaturated bond that is a radical polymerizable site.
  • the polymerizable compound in the present invention means a compound that is not a so-called non-reactive polymer substance, and therefore includes not only a monomer compound (monomer) in a narrow sense, but also a dimer, a trimer, It also includes oligomers and reactive polymers.
  • Examples of such a polymerizable compound include a compound having a radically polymerizable site or a cationically polymerizable site.
  • Examples of the polymerizable compound having a radical polymerizable site include a compound having an ethylenically unsaturated bond.
  • Examples of the polymerizable compound having a cationically polymerizable site include a compound having a vinyl thioether structure or a cyclic ether structure such as an epoxy ring or an oxetane ring.
  • Examples of the compound having an ethylenically unsaturated bond include: unsaturated carboxylic acid; unsaturated carboxylic acid ester compound; ester compound of aliphatic polyhydroxy compound and unsaturated carboxylic acid; aromatic polyhydroxy compound and unsaturated carboxylic acid An ester compound obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polyvalent carboxylic acid; and an alkylene oxide-modified product thereof. (Modified products of ethylene oxide, propylene oxide, etc.).
  • unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.
  • the unsaturated carboxylic acid ester compound examples include acrylic acid ester compounds such as phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and isobornyl acrylate.
  • acrylic acid ester compounds such as phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and isobornyl acrylate.
  • methacrylic acid ester compounds in which the acrylate moiety of these exemplified compounds is replaced with methacrylate, itaconic acid ester compounds similarly replaced with itaconate, crotonic acid ester compounds replaced with crotonate, and maleic acid ester compounds replaced with maleate are also included. No.
  • ester compound of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol
  • Acrylic ester compounds such as triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol polyacrylate are exemplified.
  • methacrylic acid ester compounds in which the acrylate portion of these exemplified compounds is replaced with methacrylate itaconic acid ester compounds similarly replaced with itaconate, crotonic acid ester compounds replaced with crotonate, maleic acid ester compounds replaced with maleate, etc.
  • ester compound of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • ester compound obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polyvalent carboxylic acid
  • the ester compound is not necessarily a single substance, but is typically used.
  • Specific examples include condensates of acrylic acid and phthalic acid with ethylene glycol, condensates of acrylic acid and maleic acid with diethylene glycol, condensates of methacrylic acid and terephthalic acid with pentaerythritol, acrylic acid and adipic acid And butanediol and glycerin.
  • urethane compounds that can be obtained by reacting a polyvalent isocyanate with a hydroxyalkyl unsaturated carboxylic acid ester, or a polyvalent epoxy compound and a hydroxyalkyl unsaturated carboxylic acid
  • examples include compounds that can be obtained by reaction with an acid ester.
  • the urethane compound include, for example, EBECRYL (registered trademark) series urethane acrylate manufactured by Daicel Cytec Co., Ltd. Specifically, for example, by using EBECRYL8301, etc., excellent dispersibility is obtained without impairing dispersibility. Diffraction efficiency can be obtained.
  • Other examples of the compound having an ethylenically unsaturated bond used in the present invention include an allyl ester compound such as diallyl phthalate; and a vinyl group-containing compound such as divinyl phthalate.
  • an acrylate compound and a methacrylate compound, and their alkylene oxide modified products (ethylene oxide modified product, propylene oxide modified product, etc.) can be particularly preferably used.
  • alkylene oxide modified products ethylene oxide modified product, propylene oxide modified product, etc.
  • polyfunctional (meth) acrylate compounds which are ester compounds of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and alkylene oxide-modified products thereof (ethylene oxide-modified products, propylene oxide-modified products, etc.).
  • These compounds having an ethylenically unsaturated bond may be used alone, or may be used as a mixture if necessary.
  • ⁇ Polymerizable compound having cationically polymerizable site examples include diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, and trimethylolpropane polyglycidyl.
  • Ether resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester , Dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexanedi Ricidyl ether, 4,4'-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl 3 ', 4'- Epoxycyclohexanecarboxylate, 3,4-epoxycyclohe
  • Examples of the compound having an oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3,3-diethyloxetane, and 3-ethyl-3- (2-ethylhexyloxy Compounds having one oxetane ring such as methyl) oxetane; 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, di (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol Examples thereof include compounds having two or more oxetane rings such as tetrakis (3-ethyl-3-oxetanylmethyl) ether.
  • These polymerizable compounds having a cationically polymerizable site may be used alone, or may be used as a mixture if necessary.
  • the polymerizable compound different from the component (b): component (a) may be used alone or in combination of two or more.
  • component (b) a compound having one polymerizable site and a compound having two or more polymerizable sites (bifunctional or more polymerizable compound) may be used in combination.
  • the amount (mass) used is 10 times the mass of the total mass of the composition excluding the bifunctional or higher functional polymerizable compound. (Mass) is preferred.
  • the amount of the bifunctional or higher functional polymerizable compound is more than this ratio, the dispersion amount of (c) the triazine ring-containing hyperbranched polymer becomes relatively small, and good characteristics such as diffraction efficiency may not be obtained in some cases. Note the points.
  • the bifunctional or higher functional polymerizable compound include the compounds having two or more polymerizable sites in the above-mentioned compounds having a radical polymerizable site or compounds having a cationic polymerizable compound.
  • the polymerizable compound different from the components (b) and (a) it is particularly preferable to use a polyfunctional (meth) acrylate and an alkylene oxide-modified product thereof.
  • the composition for a volume hologram recording material of the present invention contains (c) a triazine ring-containing hyperbranched polymer as an essential component.
  • the amount of the component (c) contained in the composition for a volume hologram recording material of the present invention is such that the component (c) accounts for the total volume of the component (a), the component (b), and the component (c).
  • the ratio is preferably 3% by volume or more and 50% by volume or less, more preferably 15% by volume or more and 50% by volume or less.
  • R and R ′ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited. However, the number of carbon atoms is preferably from 1 to 20, and in consideration of further increasing the heat resistance of the polymer, the number of carbon atoms is preferably 1 to 20. It is more preferably from 10 to 1, and still more preferably from 1 to 3. Further, the structure may be linear, branched or cyclic.
  • alkyl group examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl Cyclopropyl group, 2-methylcyclopropyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2 -Dimethylpropyl, 1-ethylpropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclo Propyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methylpe Butyl
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms, and is preferably 1 to 10 carbon atoms in consideration of further increasing the heat resistance of the polymer. More preferably, it is more preferably 1-3.
  • the structure of the alkyl moiety may be linear, branched or cyclic.
  • alkoxy group examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 1-methyl Butoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexyloxy , 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethyl Butoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy 1-ethylbutoxy group, 2-ethylbutoxy group, 1,1,2-trimethylpropoxy group, 1,2,2-trimethylpropoxy group, 1-ethyl-1-methylpropoxy group, 1-ethylbutoxy
  • the number of carbon atoms of the aryl group is not particularly limited, it is preferably 6 to 40 carbon atoms. In consideration of further increasing the heat resistance of the polymer, the aryl group has 6 to 16 carbon atoms. More preferably, it is more preferably 6 to 13.
  • aryl group examples include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxy Phenyl, p-nitrophenyl, p-cyanophenyl, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, Examples thereof include a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.
  • the number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched, or cyclic. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl And 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, ⁇ -naphthylmethyl and the like.
  • Ar represents at least one divalent group selected from the group represented by the following formulas (2) to (13).
  • R 1 to R 92 each independently have a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, or a branched structure having 1 to 10 carbon atoms.
  • R 93 and R 94 each have a hydrogen atom or a branched structure having 1 to 10 carbon atoms.
  • W 1 and W 2 are each independently a single bond, CR 95 R 96 (wherein R 95 and R 96 are each independently a hydrogen atom or a carbon atom having 1 carbon atom.
  • the alkyl group and the alkoxy group include the same groups as those described above.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X 1 and X 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a compound represented by the formula (14)
  • R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom
  • R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom
  • Y 1 and Y 2 may each independently have a single bond or a branched structure having 1 to 10 carbon atoms.
  • Represents a group represented by Examples of the halogen atom, alkyl group and alkoxy group include the same groups as those described above.
  • Examples of the alkylene group which may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and the like.
  • Suitable Ar in the formula (1) in the present invention includes at least one selected from the groups represented by the formulas (2) and (5) to (13), and the formulas (2) and (5) , (7), (8), and at least one selected from the groups represented by (11) to (13).
  • aryl group (Ar) represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulas.
  • an aryl group represented by the following formula is more preferable because a hyperbranched polymer that expresses a higher refractive index can be obtained.
  • a preferred repeating unit structure contained in the triazine ring-containing hyperbranched polymer is a repeating unit structure represented by the formula (1), wherein Ar is a divalent group represented by the formula (2). Certain of them, that is, a repeating unit structure represented by the following formula (15) is preferable. (In the formula, R, R ′ and R 1 to R 4 represent the same meaning as described above.)
  • a repeating unit structure represented by the following formula (16) can be mentioned, and among them, a triazine ring-containing hyperbranched polymer containing a repeating unit structure represented by the following formula (17) is most suitable. is there.
  • the weight average molecular weight of the triazine ring-containing hyperbranched polymer (c) in the present invention is not particularly limited, but is preferably from 500 to 500,000, more preferably from 500 to 100,000. In view of lowering the shrinkage, 2,000 or more is preferable, and 50,000 or less is preferable, and 30,000 or less is more preferable, from the viewpoint of increasing the solubility and lowering the viscosity of the obtained solution. And more preferably 10,000 or less.
  • the weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter, referred to as GPC) analysis in terms of standard polystyrene.
  • the triazine ring-containing hyperbranched polymer (c) can be produced by the method disclosed in WO 2010/128661. For example, as shown in the following Scheme 1, a repeating unit structure (17) is obtained by reacting a cyanuric halide (18) and an m-phenylenediamine compound (19) in an appropriate organic solvent. ') A triazine ring-containing hyperbranched polymer having ()) can be obtained.
  • photopolymerization initiator As the photopolymerization initiator in the present invention, a function capable of initiating polymerization of a polymerizable compound different from the component (a) and / or the component (b) by the pattern exposure described in detail below. There is no particular limitation as long as the compound has Component (b): When a compound having an ethylenically unsaturated bond, which is a radical polymerizable site, is used as a polymerizable compound different from component (a), the photopolymerization initiator is basically a pattern exposure. A photo-radical polymerization initiator that sometimes generates an active radical is used.
  • the photopolymerization initiator may be: Basically, a photoacid generator that generates a Lewis acid or Bronsted acid during pattern exposure is used.
  • the photo-radical polymerization initiator is not particularly limited as long as it is a compound that generates an active radical at the time of pattern exposure.
  • Examples thereof include a benzoin compound, an ⁇ -aminoalkylphenone compound, an N-aryl- ⁇ -amino acid compound, and thioxanthone.
  • Photoradical polymerization initiator may be used alone, or may be used as a mixture of two or more as needed.
  • the titanocene compound is not particularly limited.
  • the N-aryl- ⁇ -amino acid-based compound is not particularly limited.
  • the trichloromethyltriazine-based compound is not particularly limited.
  • benzoin-based compound examples include benzoin ethyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON etc. can be mentioned.
  • Examples of the ⁇ -aminoalkylphenone-based compound include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butan-1-one and the like.
  • thioxanthone compounds include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethyl Thioxanthone and the like can be mentioned.
  • Examples of the azo compound include 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), and 2,2′-azobis (N- (2-carboxyethyl) -2-methylpropionamidine), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methyl-N- (2- (1-hydroxybutyl)) ) Propionamide), 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), 2,2′-azobis (2- (5-methyl-2-imidazoline-2-i) ) Propane) hydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl
  • azide compound examples include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidediphenyl sulfide, , 6-bis (4'-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidostilbene and the like.
  • diazo compound examples include 2,5-diethoxy-4-p-tolylmercaptobenzenediazonium tetrafluoroborate, 4- (dimethylamino) benzenediazonium chloride, and 4- (diethylamino) benzenediazonium tetrafluoroborate. it can.
  • Examples of the o-quinonediazide compound include 1,2-naphthoquinonediazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester, and 1,2-naphthoquinonediazide (2 ) -4-sulfonyl chloride and the like.
  • acylphosphine oxide compounds include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.
  • oxime ester compounds examples include 2- (O-benzoyloxime) -1- (4- (phenylthio) phenyl) -1,2-octanedione and 1- (O-acetyloxime) -1- (9-ethyl And -6- (2-methylbenzoyl) -9H-carbazol-3-yl) ethanone.
  • benzophenones include benzophenone, 4,4'-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, and 4-benzoyl Examples thereof include diphenyl ether and 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone.
  • Biscoumarin includes, for example, 3,3'-carbonylbis (7-diethylaminocoumarin), which is commercially available as BC (CAS [63226-13-1]) from Midori Kagaku.
  • bisimidazole compound examples include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) -1,2′-biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.
  • boron compound examples include, but are not particularly limited to, trialkyl borons such as triethyl boron, tripropyl boron, tributyl boron, trihexyl boron, and tricyclohexyl boron; and triaryl borons such as triphenyl boron and trinaphthyl boron.
  • trialkyl borons such as triethyl boron, tripropyl boron, tributyl boron, trihexyl boron, and tricyclohexyl boron
  • triaryl borons such as triphenyl boron and trinaphthyl boron.
  • Alkoxydialkylborons such as ethoxydiethylboron, propoxydipropylboron and butoxydibutylboron; and alkyltriarylborates (such as butyltriphenylborate and butyltrinaphthylborate); and dialkyldiarylborates (dibutyldiphenylborate and dibutyldinaphthyl).
  • Borates such as trialkylaryl borates (such as tributyl phenyl borate and tributyl naphthyl borate).
  • Lithium, potassium, magnesium, etc. ammonium salts (tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.), pyridinium salts (methylpyridinium, ethylpyridinium, butylpyridinium, etc.), quinolinium salts (methylquinolinium, ethylquinolinium) Butylquinolinium), phosphonium salts, sulfonium salts and the like.
  • titanocene compounds N-aryl- ⁇ -amino acid compounds, and trichloromethyltriazine compounds are preferred.
  • titanocene compounds bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium is replaced with N-aryl- ⁇ -amino acid-based compound.
  • Preferred examples of phenylglycine include 2,4,6-tris (trichloromethyl) -1,3,5-triazine among trichloromethyltriazine-based compounds.
  • N-phenylglycine may be used in combination with a sensitizer such as rose bengal or 3,3′-dipropylthiazicarbocyanine iodide described later, and 2,4,6-tris (trichloromethyl)- 1,3,5-Triazine may be used in combination with a sensitizer such as 3,3'-dipropylthiazicarbocyanine iodide described below.
  • the photoacid generator is not particularly limited as long as it is a compound that generates a Lewis acid or a Bronsted acid at the time of pattern exposure.
  • diaryliodonium salt compounds, triarylsulfonium salt compounds, onium salt compounds such as diazonium salt compounds, Iron arene complex compounds and the like can be mentioned.
  • diaryliodonium salt compound examples include diphenyliodonium, 4,4'-dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tert-butyldiphenyliodonium, (4-methylphenyl)
  • iodonium such as 4- (2-methylpropyl) phenyl) iodonium and 3,3′-dinitrophenyliodonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
  • triarylsulfonium salt compound examples include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, and diphenyl (4-phenylthiophenyl) )
  • sulfonium such as sulfonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
  • iron arene complex compound examples include biscyclopentadienyl- ( ⁇ 6 -isopropylbenzene) -iron (II) hexafluorophosphate.
  • photopolymerization initiators such as the photoradical polymerization initiator and the photoacid generator may be used alone, or may be used as a mixture of two or more as needed.
  • the blending amount of the photopolymerization initiator in the composition for a volume hologram recording material of the present invention is 0.01 to the total amount of the component (a) and the component (b): the total amount of the polymerizable compound different from the component (a). To 10% by mass, preferably 0.05 to 5% by mass.
  • volume hologram recording medium containing the composition for a volume hologram recording material containing the components (a) to (d), and a volume hologram recording medium containing the recording layer.
  • the recording layer of the volume hologram recording medium of the present invention may contain, if necessary, additives such as a sensitizer, a chain transfer agent, a plasticizer, and a coloring agent in addition to the components (a) to (d). Is also good.
  • a sensitizer can be used to increase the sensitivity of the photopolymerization initiator to light.
  • the sensitizer include 2,6-diethyl-1,3,5,7,8-pentamethylpyrromethene-BF 2 complex and 1,3,5,7,8-pentamethylpyrromethene-BF 2 Pyrromethene complex compounds such as complexes; xanthene dyes such as eosin, ethyl eosin, erythrosine, fluorescein, and rose bengal; 3,3′-diethyloxacarbocyanine iodide, 3,3′-diethylthiacarbocyanine iodide; 3′-diethyloxadicarbocyanine iodide, 3,3′-dipropylthiazicarbocyanine iodide, 3,3,3 ′, 3′-tetramethyl-1,1′-bis (4-sulfobutyl) benzo
  • a sensitizer it is added in an amount of, for example, 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 1 part by mass of the photopolymerization initiator (d). is there.
  • a binder resin may be added as a binder in order to have a uniform film thickness and stably exist an interference film formed by polymerization by light irradiation.
  • the binder resin preferably has good compatibility with the resin components (components (a) and (b)), and specific examples thereof include chlorinated polyethylene, polymethyl (meth) acrylate, methyl (meth) acrylate, and other (meth) acrylates.
  • Copolymers of acrylic acid alkyl esters Copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, acetyl cellulose and the like.
  • the components (a) to (d) are mixed with a sensitizer, a binder resin and the like, if necessary. It is applied as it is on a transparent substrate (support) without solvent, or a mixture of these is added with a solvent or an additive to form a so-called varnish, which is coated on the transparent substrate and dried to form a varnish on the transparent substrate.
  • a recording medium on which a volume hologram recording layer is formed is obtained.
  • a transparent substrate or a protective layer for blocking oxygen may be provided on the recording layer, and the volume hologram recording layer may be arranged between two transparent substrates or between the transparent substrate and the protective layer.
  • the solvent is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties.
  • propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; Butyl acetate, amyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl pyruvate, 2-hydroxy Ester solvents such as ethyl acetate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate; alcohol solvents such as butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; methyl isobutyl ketone
  • a transparent substrate a transparent glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene film or the like is used.
  • a coating method a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, or the like can be used.
  • the protective layer As the protective layer, a known technique for preventing adverse effects such as a decrease in sensitivity and a deterioration in storage stability due to oxygen, for example, a coating of a water-soluble polymer or the like can be used.
  • the present invention is also directed to a pattern forming method using the composition for a volume hologram recording material. That is, a method including a step of applying the composition for a volume hologram recording material to a support to form a coating film, and a step of pattern-exposing the coating film, and in particular, the pattern exposure is interference exposure. Is preferred.
  • a method including a step of applying the composition for a volume hologram recording material to a support to form a coating film, and a step of pattern-exposing the coating film, and in particular, the pattern exposure is interference exposure.
  • the above-mentioned support those mentioned above as the transparent substrate can be suitably used, and as the method of coating on the support, the above-mentioned method of coating on the transparent substrate can be mentioned.
  • a composition for volume hologram recording a composition composed of a plurality of functional monomers having different refractive indices, a composition composed of a liquid organic substance and a functional monomer, and the like are conventionally known.
  • the refractive index of conventionally proposed organic substances is usually limited to about 1.3 to 1.6, and it is said that there is a limit to increasing the refractive index difference in a hologram recording material composed of a combination of organic substances.
  • the triazine ring-containing hyperbranched polymer used in the present invention has a high refractive index exceeding 1.7, and therefore has a large refractive index difference even in combination with an organic substance (such as a resin component) which has been regarded as having a limit in the past. Therefore, a hologram having a high diffracted light rate can be obtained.
  • a pattern such as a hologram is formed by recording an interference pattern of light using a difference in refractive index between at least two kinds of components included in the recording layer due to mutual diffusion of interference fringes into bright and dark portions.
  • the above-mentioned hydroxyalkyl (meth) acrylate and other polymerizable It is important that the difference between the refractive index of a polymer formed from a polymerizable component such as a compound and the refractive index of a triazine ring-containing hyperbranched polymer is large.
  • the refractive index of the triazine ring-containing hyperbranched polymer and the polymerization of hydroxyalkyl (meth) acrylate and other polymerizable compounds are determined with respect to the wavelength of light used for interference exposure for hologram recording. It can be said that it is preferable that the difference from the refractive index of the polymer generated from the acidic component is large. For example, it is preferable that the difference be 0.01 to 0.6. Further, it can be said that the difference in the refractive index is more preferably 0.02 to 0.5 or 0.03 to 0.4.
  • the refractive index of the (meth) acrylate polymer is 1.49 to 1.53, and the refractive index of the epoxy polymer is 1.55 to 1.61.
  • the aforementioned component that is, the (b) triazine ring-containing hyperbranched polymer suitable for use in the present invention and the polymerizable component (particularly, the (b) polymerized Compounds) are selected.
  • the refractive index of the triazine ring-containing hyperbranched polymer is relatively high, and for example, the refractive index with respect to light having a wavelength of 589 nm exceeds 1.7.
  • the refractive index of the polymer produced from the polymerizable component (hydroxyalkyl (meth) acrylate and a polymerizable compound different therefrom) used in the present invention is relatively smaller than the above value,
  • a polymerizable component that gives a polymer having a refractive index of 1.3 to 1.7 with respect to light having a wavelength of 589 nm is preferably used.
  • a polymerizable component (such as a polymerizable compound) that gives a polymer having a refractive index of 1.3 to 1.6 with respect to light having a wavelength of 589 nm is used.
  • the refractive index of the polymer after applying a composition comprising a polymerizable component and a photopolymerization initiator on a support, drying if necessary, and then using light used for interference exposure for hologram recording.
  • the polymer can be obtained by subjecting the composition to spatially uniform exposure under the conditions used, and can be determined by measuring the refractive index of the polymer. Then, based on the refractive index of the polymer thus obtained and the refractive index of the triazine ring-containing hyperbranched polymer, a polymerizable component ((meth) acrylic) suitable for the hologram recording material composition of the present invention is used. Hydroxyalkyl acid and a polymerizable compound different therefrom), and a triazine ring-containing hyperbranched polymer.
  • Measurement solvent DMSO-d 6 Reference substance: tetramethylsilane ( ⁇ 0.00ppm) [GPC (gel permeation chromatography)] Apparatus: Tosoh Corporation HLC-8200GPC Column: Shodex (registered trademark) GPC KF-804L + KF-805L manufactured by Showa Denko KK Column temperature: 40 ° C Solvent: THF Detector: UV (254 nm) Calibration curve: standard polystyrene [membrane density] Apparatus: Multipurpose X-ray diffractometer D8 DISCOVER manufactured by Bruker Japan Tube voltage-current: 50kV-100mA Measuring range: 0.2-3.0 deg (2 ⁇ ) Step width: 0.005 deg (2 ⁇ ) time / step: 0.5 seconds / step [5% weight loss temperature (Td 5% )] Apparatus: Rigaku Corporation Differential thermal balance (TG-DTA) TG-8120 Heating rate: 10 ° C / min Measure
  • the reaction solution was added dropwise to 622 g of DMAc in a 2 L four-necked flask, which was separately heated to 85 ° C. by an oil bath, over 1 hour using a liquid sending pump, and further stirred for 1 hour to polymerize. Thereafter, 113.95 g (1.224 mol) of aniline was added, and the mixture was further stirred for 1 hour to complete the reaction. Cooled to room temperature (approximately 23 ° C.) with an ice bath. After 116.36 g (1.15 mol) of triethylamine was added dropwise thereto, the mixture was further stirred for 30 minutes to quench hydrochloric acid by-produced by the polymerization reaction.
  • the precipitated hydrochloride was filtered off.
  • the filtrate was added to a mixed solution of 279.29 g of a 28% by mass aqueous ammonia solution and 8,820 g of ion-exchanged water to reprecipitate a polymer.
  • the precipitate was collected by filtration and dried under reduced pressure at 150 ° C. for 8 hours.
  • the obtained crude product was redissolved in 833 g of THF, added to 6,665 g of ion-exchanged water, and reprecipitated.
  • the precipitate was collected by filtration, and dried under reduced pressure at 150 ° C.
  • FIG. 1 shows the 1 H NMR spectrum of the obtained HB-TmDA.
  • HB-TmDA is a compound having a repeating unit structure represented by the above formula [1a].
  • the weight average molecular weight Mw measured by GPC of HB-TmDA in terms of polystyrene is 4,300
  • the polydispersity Mw / Mn is 3.4
  • the 5% weight loss temperature Td 5% is 419 ° C.
  • the density of HB-TmDA obtained from the film density measurement was 1.32 g / cm 3 .
  • the obtained HB-TmDA 10% by mass cyclohexanone solution was spin-coated (200 rpm ⁇ 5 seconds, then 2,000 rpm ⁇ 30 seconds) on a glass substrate, and heated at 150 ° C. for 1 minute and then at 250 ° C. for 5 minutes. To form a coating film.
  • the refractive index of the obtained coating film at 550 nm was 1.790.
  • composition for volume hologram recording material (A) 764 mg of 4HBA as hydroxyalkyl (meth) acrylate, (b) 303 mg of DPHA as a polymerizable compound, (c) 320 mg of HB-TmDA obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, and (d) As a photopolymerization initiator, 3.1 mg of I784 was mixed and stirred at 50 ° C. for 72 hours to prepare a composition for a volume hologram recording material.
  • the density of 4HBA is 1.04 g / cm 3
  • HB-TmDA is 1.32 g / cm 3, respectively its volume
  • 4HBA: 0.764 ⁇ 1.04 0.735 cm 3
  • DPHA: 0.303 ⁇ 1.186 0.255 cm 3
  • HB-TmDA: 0.32 ⁇ 1.32 0.242 cm 3 .
  • ⁇ Preparation of volume hologram recording medium> A metal foil having a thickness of 10 ⁇ m is placed as a spacer on the upper, lower, left, and right ends of the slide glass, and the above-described composition for a volume hologram recording material is dropped at the center of the slide glass (an area sandwiched by the spacers) to form a volume hologram recording layer. did. Thereafter, another slide glass was placed so as to sandwich the formed volume hologram recording layer, thereby producing a volume hologram recording medium.
  • the obtained volume hologram recording medium was subjected to two-beam interference exposure using the apparatus shown in FIG. 2 to attempt to record a volume hologram.
  • Two- beam interference exposure (lattice interval: 1 ⁇ m) was performed on the volume hologram recording medium at an exposure power density of 250 mW / cm 2 using an Nd: YVO 4 laser having a wavelength of 532 nm.
  • the light emitted from the Nd: YVO 4 laser is split into two beams by a half mirror via a beam expander, and is irradiated on a volume hologram recording medium via each mirror, and interference fringes of both lights are recorded to form a volume hologram.
  • a helium-neon (He-Ne) laser having a wavelength of 632.8 nm to which the volume hologram recording medium is not exposed is irradiated on the volume hologram recording medium, and the diffracted light is detected by a photodetector to monitor the hologram formation process and diffract.
  • the efficiency was evaluated.
  • the angle dependence of the diffraction efficiency after exposure was measured, and the film thickness of the sample after exposure was calculated. Further, based on the obtained diffraction efficiency and film thickness, the change in exposure time of the refractive index modulation amount ( ⁇ n) and the saturated refractive index modulation amount ( ⁇ n sat ) were evaluated.
  • the results are shown in Table 1.
  • FIG. 3 shows a change in ⁇ n with respect to the exposure time.
  • the composition of the present invention (Example 1) has an extremely high saturation refraction as compared with the composition in which an acrylic monomer having an ether structure and a vinyl monomer having an amide structure are added (Comparative Example 1). It was confirmed that the rate modulation amount ⁇ n sat was exhibited.
  • a composition containing an unsubstituted alkyl (meth) acrylate (Comparative Example 2) and a composition containing an aralkyl (meth) acrylate (Comparative Example 3) were used. Obtained a result that the hyperbranched polymer did not dissolve and a uniform composition was not obtained.
  • Example 2 (A) 4,918 mg of 4HBA as hydroxyalkyl (meth) acrylate, (b) 159 mg of EDPHA as a polymerizable compound, (c) 913 mg of HB-TmDA obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, and ( d) 6.36 mg of NPG as a photopolymerization initiator and 3.18 mg of RB as a sensitizer were mixed and stirred at 50 ° C. for 24 hours to prepare a composition for a volume hologram recording material.
  • a volume hologram recording medium was prepared in the same manner as in Example 1 except that the thickness of the spacer was changed to 5 ⁇ m and the exposure power density was changed to 5 mW / cm 2 , and the refractive index modulation was performed.
  • the exposure time change of the amount ( ⁇ n) and the saturated refractive index modulation amount ( ⁇ n sat ) were evaluated. The results are shown in Table 2.
  • FIG. 5 shows a change in ⁇ n with respect to the exposure time.
  • the density of 4HBA is 1.04 g / cm 3
  • the density of EDPHA is 1.15 g / cm 3
  • the density of HB-TmDA is 1.32 g / cm 3
  • the volumes are 4HBA: 3.918, respectively.
  • ⁇ 1.04 3.767 cm 3
  • EDPHA: 0.159 ⁇ 1.15 0.138 cm 3
  • HB-TmDA: 0.913 ⁇ 1.32 0.692 cm 3
  • Examples 3 to 5 In the same manner as in Example 2, a volume hologram medium in which the volume fraction of HB-TmDA had the value shown in Table 2 was produced and evaluated in the same manner. The results are shown in Table 2. 6 (Example 3), FIG. 7 (Example 4), and FIG. 8 (Example 5) show changes in ⁇ n with respect to the exposure time.
  • compositions of the present invention (Examples 2 to 5) exhibited an extremely high saturation refractive index modulation amount ⁇ n sat , and (b) ethylene oxide-modified dipentaerythritol as a polymerizable compound
  • hexaacrylate (d) N-phenylglycine as a photopolymerization initiator and rose bengal as a sensitizer, the composition of Example 1 ((b) dipentaerythritol pentaacrylate / diacrylate as a polymerizable compound) was used.
  • Example 6 (A) 3,632 mg of 4HBA as hydroxyalkyl (meth) acrylate, (b) 157 mg of EDPHA as a polymerizable compound, (c) 1,202 mg of HB-TmDA obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, Further, (d) 23.56 mg of TCT as a photopolymerization initiator and 3.14 mg of DiSC as a sensitizer were mixed and stirred at 50 ° C. for 24 hours to prepare a composition for a volume hologram recording material.
  • the density of 4HBA is 1.04 g / cm 3
  • the density of EDPHA is 1.15 g / cm 3
  • the density of HB-TmDA is 1.32 g / cm 3
  • the volumes are 4HBA: 3.632.
  • ⁇ 1.04 3.492 cm 3
  • EDPHA: 0.157 ⁇ 1.15 0.136 cm 3
  • HB-TmDA: 1.202 ⁇ 1.32 0.911 cm 3
  • a volume hologram recording medium was produced in the same manner as in Example 1 except that the thickness of the spacer was changed to 5 ⁇ m.
  • the obtained volume hologram recording medium was subjected to two-beam interference exposure using the apparatus shown in FIG. 9 to attempt to record a volume hologram.
  • Two- beam interference exposure (grating interval: 0.5 ⁇ m) was performed on the volume hologram recording medium with an exposure power density of 5 mW / cm 2 using a solid-state laser having a wavelength of 640 nm [05-01 Bolero, manufactured by Cobolt].
  • the light emitted from the solid-state laser was split into two light beams by a half mirror via a beam expander, and was applied to the volume hologram recording medium via the respective mirrors.
  • Nd wavelength 532nm of the volume hologram recording medium is not sensitive: a YVO 4 laser is irradiated to the volume hologram recording medium was evaluated monitored diffraction efficiency of the hologram formation process by detecting the diffracted light by the photodetector. The angle dependence of the diffraction efficiency after exposure was measured, and the film thickness of the sample after exposure was calculated. Further, based on the obtained diffraction efficiency and film thickness, the change in exposure time of the refractive index modulation amount ( ⁇ n) and the saturated refractive index modulation amount ( ⁇ n sat ) were evaluated. The results are shown in Table 3.
  • FIG. 10 shows a change in ⁇ n with respect to the exposure time.
  • composition for a volume hologram recording material of the present invention and the volume hologram recording medium obtained therefrom can be used for three-dimensional image display, wearable display, large-capacity bit information memory, diffractive optical element, and the like.

Abstract

[Problem] To provide: a volume hologram-recording material branch composition capable of permanently forming holograms having extremely low light scattering loss and high diffraction efficiency; and a hologram recording medium using the composition. [Solution] The present invention provides: a volume hologram-recording material composition used for forming a pattern by pattern exposure, the composition containing (a) hydroxyalkyl (meth)acrylate, (b) a polymerizable compound other than component (a), (c) a triazine ring-containing hyperbranched polymer, and (d) a photopolymerization initiator; and a hologram recording medium using the composition.

Description

トリアジン環含有ハイパーブランチポリマーを含む体積ホログラム記録材料用組成物Composition for volume hologram recording material containing triazine ring-containing hyperbranched polymer
　本発明は、パターン露光することにより、組成物中の各成分に移動が生じ、各成分の空間分布が変化したパターンを形成できる体積ホログラム記録材料用組成物、及び該組成物を用いたパターンの形成方法に関する。また、当該ホログラム記録材料用組成物を含む体積ホログラム記録層並びに当該記録層を備える体積ホログラム記録媒体に関する。 The present invention provides a composition for a volume hologram recording material capable of forming a pattern in which each component in the composition is moved by pattern exposure, and a spatial distribution of each component is changed, and a pattern using the composition. It relates to a forming method. The present invention also relates to a volume hologram recording layer containing the hologram recording material composition and a volume hologram recording medium provided with the recording layer.
　ホログラフィック回折格子（ホログラム）は、光の明暗（干渉）パターンを感光材料等に屈折率あるいは吸収率のパターンとして記録したものであり、多機能を有することから回折光学素子、ホログラフィック光メモリ、狭帯域波長フィルター、フォトニック結晶、光導波路結合器、光インターコネクション、立体画像ディスプレイ、ヘッドアップディスプレイなど、フォトニクスや情報ディスプレイ等の幅広い分野において数多くの応用が報告されている。これら応用分野では、通常、大きな屈折率変化と高い記録感度が要求される。 A holographic diffraction grating (hologram) is a pattern in which a light / dark (interference) pattern of light is recorded as a pattern of a refractive index or an absorptance on a photosensitive material or the like. Numerous applications have been reported in a wide range of fields such as photonics and information displays, such as band wavelength filters, photonic crystals, optical waveguide couplers, optical interconnections, stereoscopic image displays, head-up displays, and the like. In these application fields, a large change in the refractive index and a high recording sensitivity are usually required.
　従来の代表的なホログラム記録材料用組成物としては、重クロム酸ゼラチン感光材料や、漂白処理した銀塩感光材料が使用されてきた。これらは高い回折効率を持つが、ホログラム作成時の処理が複雑で、特に湿式現像処理が必要であるという欠点があった。
　かかる欠点を克服する乾式のホログラム感光材料として、デュポン社のオムニデックスシリーズが広く知られている。この材料はラジカル重合モノマーとバインダーポリマー、光ラジカル重合開始剤及び増感色素を主成分として、ラジカル重合モノマーとバインダーポリマーの屈折率差を利用してホログラムを記録するものである。すなわち、フィルム状に形成された該感光性組成物を干渉露光すると、光が強い部分にてラジカル重合が開始され、それに伴いラジカル重合モノマーの濃度勾配ができ、光が弱い部分から強い部分にラジカル重合モノマーの拡散移動が起こる。結果として干渉光の強弱に応じて、ラジカル重合モノマー密度及び重合したポリマーの密度の疎密ができ、それらとバインダーポリマーの屈折率の差としてホログラムが形成される。この材料系は現状報告されているホログラム用フォトポリマーとしては高性能であるが、３０μｍ程度の厚みに限定されること、そして、耐熱性、透明性に問題がある点が指摘されている。 As typical conventional compositions for hologram recording materials, a dichromated gelatin photosensitive material or a bleached silver salt photosensitive material has been used. These have a high diffraction efficiency, but have a drawback that the processing at the time of forming the hologram is complicated and particularly requires wet development processing.
As a dry-type hologram photosensitive material that overcomes such a disadvantage, the Omnidex series of DuPont is widely known. This material records a hologram using a radical polymerization monomer, a binder polymer, a photoradical polymerization initiator, and a sensitizing dye as main components and utilizing a difference in refractive index between the radical polymerization monomer and the binder polymer. That is, when the photosensitive composition formed in the form of a film is subjected to interference exposure, radical polymerization is started in a portion where light is strong, and a concentration gradient of a radical polymerization monomer is generated with the exposure. Diffusion transfer of the polymerized monomer occurs. As a result, the density of the radical polymerized monomer and the density of the polymerized polymer vary depending on the intensity of the interference light, and a hologram is formed as the difference between the refractive index of the polymer and the refractive index of the binder polymer. Although this material system has high performance as a hologram photopolymer that is currently reported, it is pointed out that the thickness is limited to about 30 μm, and there are problems in heat resistance and transparency.
　また、ラジカル重合とカチオン重合を併用した材料系（特許文献１参照）や、カチオン重合を利用した材料系（特許文献２参照）が報告されているが、これらはお互いのポリマー同士が分子レベルで相溶しないため、この材料系で形成されたホログラム記録膜は相分離による透明性の低下が生じ、それに基づく散乱損失の増大などの問題点がある。さらに機械的強度及び環境安定性に関し未だ不十分である。 In addition, a material system using both radical polymerization and cationic polymerization (see Patent Document 1) and a material system using cationic polymerization (see Patent Document 2) have been reported. Since they are not compatible, the hologram recording film formed of this material system has a problem that transparency is reduced due to phase separation, and scattering loss is increased due to this. Furthermore, the mechanical strength and environmental stability are still insufficient.
　また、無機物質ネットワークと光重合性モノマーを併用した材料系が開示されている（特許文献３参照）。ネットワークを形成し得る無機材料をバインダーとして用いる場合には、耐熱性、対環境性、機械強度に優れると共に、光重合性の有機モノマーとの屈折率差を大きく取れるという利点があるが、この材料系で形成したホログラム記録膜はどちらかと言えば脆く、柔軟性や加工性、コーティング適性に劣るという問題点、及び無機バインダーと有機モノマーとの相溶性が悪く均一な塗工材料を調製するのが困難という問題点がある。 材料 Also, a material system using an inorganic substance network and a photopolymerizable monomer in combination has been disclosed (see Patent Document 3). When an inorganic material capable of forming a network is used as a binder, there is an advantage that heat resistance, environmental friendliness, and mechanical strength are excellent, and a large difference in refractive index from a photopolymerizable organic monomer can be obtained. The hologram recording film formed by the system is rather brittle and has problems such as poor flexibility, processability, and coating suitability, and poor compatibility between the inorganic binder and the organic monomer to prepare a uniform coating material. There is a problem of difficulty.
　また、固体マトリックスに金属超微粒子を分散した材料が、ホログラム記録材料として開示されている（特許文献４参照）。しかし、この発明ではマトリックスに流動性を持たせる必要があり、固体性が悪いだけでなく、金属粒子界面と固体マトリックスとの界面密着性が悪く、脆く、界面へ水が侵入するなどの問題がある。 材料 Further, a material in which ultrafine metal particles are dispersed in a solid matrix is disclosed as a hologram recording material (see Patent Document 4). However, in this invention, it is necessary to impart fluidity to the matrix, and not only poor solidity, but also poor adhesion between the metal particle interface and the solid matrix, brittleness, and problems such as intrusion of water into the interface. is there.
　また、有機－無機ハイブリッドポリマーと光重合反応性基を有する有機金属微粒子を用いたホログラム記録材料が開示されている（特許文献５参照）。しかし、この発明では干渉縞を固定する為に加熱及び紫外線重合が必要となり、工業プロセスとして課題がある。 Also, a hologram recording material using an organic-inorganic hybrid polymer and organometallic fine particles having a photopolymerization-reactive group has been disclosed (see Patent Document 5). However, in this invention, heating and ultraviolet polymerization are required to fix the interference fringes, and there is a problem as an industrial process.
　より簡便な方法でホログラム記録を行う材料として、無機微粒子を光重合性モノマーに分散させたホログラム記録材料が開示されている（特許文献６、特許文献７及び非特許文献１参照）。
　また、エチレン性不飽和基を有するエン化合物及びメルカプト基を有するチオール化合物の混合物に微粒子を分散することにより、低収縮なホログラム記録材料が開示されている（特許文献８）。
　さらに、トリアジン環含有ハイパーブランチポリマーを含む体積ホログラム記録材料用組成物が開示されている（特許文献９）。
　しかしこれらの材料においても、十分な回折効率が得られていないという課題がある。 As a material for performing hologram recording by a simpler method, a hologram recording material in which inorganic fine particles are dispersed in a photopolymerizable monomer is disclosed (see Patent Literature 6, Patent Literature 7, and Non-Patent Literature 1).
Further, a low-shrink hologram recording material is disclosed by dispersing fine particles in a mixture of an ene compound having an ethylenically unsaturated group and a thiol compound having a mercapto group (Patent Document 8).
Further, a composition for a volume hologram recording material containing a triazine ring-containing hyperbranched polymer is disclosed (Patent Document 9).
However, even with these materials, there is a problem that sufficient diffraction efficiency is not obtained.
特開平５－１０７９９９号公報JP-A-5-107999 米国特許第５７５９７２１号明細書U.S. Pat. No. 5,759,721 特開平６－０１９０４０号公報JP-A-6-019040 特表２０００－５０８７８３号公報JP 2000-508873 A 特開２００２－２３６４４０号公報JP-A-2002-236440 特開２００３－０８４６５１号公報JP 2003-084651 A 特開２００５－０９９６１２号公報JP 2005-099612 A 特開２０１０－２５０２４６号公報JP 2010-250246 A 特開２０１４－１９７１９１号公報JP 2014-197191 A
　本発明は、体積ホログラム記録材料において、凝集性が低く、極めて高い屈折率を有するトリアジン環含有ハイパーブランチポリマーを微粒子として用い、かつ、該ハイパーブランチポリマーを分散・溶解可能な成分として（メタ）アクリル酸ヒドロキシアルキルを他の重合性成分とともに配合することにより、光散乱損失が極めて低く、回折効率の高いホログラムを永続的に形成できる体積ホログラム記録材料用組成物、及び該組成物を用いたホログラム記録媒体を提供することを目的とする。 The present invention relates to a volume hologram recording material, wherein a triazine ring-containing hyperbranched polymer having low cohesiveness and an extremely high refractive index is used as fine particles, and (meth) acrylic is used as a component capable of dispersing and dissolving the hyperbranched polymer. A composition for a volume hologram recording material capable of permanently forming a hologram having a very low light scattering loss and a high diffraction efficiency by blending a hydroxyalkyl acid with other polymerizable components, and hologram recording using the composition The purpose is to provide a medium.
　本発明者らは、上記目的を達成するために鋭意検討を行った結果、本発明を見出すに至った。
　すなわち、第１観点として、パターン露光によってパターンを形成するために使用される体積ホログラム記録材料用組成物であって、
（ａ）（メタ）アクリル酸ヒドロキシアルキル、
（ｂ）（ａ）成分とは異なる重合性化合物、
（ｃ）トリアジン環含有ハイパーブランチポリマー及び
（ｄ）光重合開始剤
を含む体積ホログラム記録材料用組成物に関する。
　第２観点として、前記（ａ）成分、前記（ｂ）成分、及び前記（ｃ）成分の合計体積に占める前記（ｃ）成分の割合が、３体積％以上、５０体積％以下である、第１観点に記載の体積ホログラム記録材料用組成物に関する。
　第３観点として、前記パターン露光が干渉露光であり、該干渉露光によりホログラムを形成するために使用される、第１観点又は第２観点に記載の体積ホログラム記録材料用組成物に関する。
　第４観点として、前記（ｂ）（ａ）成分とは異なる重合性化合物が多官能（メタ）アクリレートである、第１観点乃至第３観点のうち何れか一項に記載の体積ホログラム記録材料用組成物に関する。
　第５観点として、第１観点乃至第４観点のうち何れか１項に記載の体積ホログラム記録材料用組成物を含む体積ホログラム記録層に関する。
　第６観点として、第５観点に記載の体積ホログラム記録層を含む体積ホログラム記録媒体に関する。
　第７観点として、体積ホログラム記録層が、各々平面を有しそれら平面が対面する２枚の透明基体間に配置された構造である、第６観点に記載の体積ホログラム記録媒体に関する。
　第８観点として、第１観点乃至第４観点のうち何れか一項に記載の体積ホログラム記録材料用組成物を、支持体に塗布し塗布膜を形成する工程、及び前記塗布膜にパターン露光する工程を含む、パターンの形成方法に関する。
　第９観点として、前記パターン露光が干渉露光である、第８観点に記載のパターンの形成方法に関する。 The present inventors have conducted intensive studies to achieve the above object, and as a result, have found the present invention.
That is, as a first aspect, a composition for a volume hologram recording material used for forming a pattern by pattern exposure,
(A) hydroxyalkyl (meth) acrylate,
(B) a polymerizable compound different from the component (a),
The present invention relates to a composition for a volume hologram recording material, comprising (c) a triazine ring-containing hyperbranched polymer and (d) a photopolymerization initiator.
As a second viewpoint, the ratio of the component (c) to the total volume of the component (a), the component (b), and the component (c) is 3% by volume or more and 50% by volume or less. The present invention relates to a composition for a volume hologram recording material according to one aspect.
As a third aspect, the present invention relates to the composition for a volume hologram recording material according to the first aspect or the second aspect, wherein the pattern exposure is interference exposure, and is used for forming a hologram by the interference exposure.
As a fourth aspect, for the volume hologram recording material according to any one of the first to third aspects, the polymerizable compound different from the components (b) and (a) is a polyfunctional (meth) acrylate. Composition.
As a fifth aspect, the present invention relates to a volume hologram recording layer including the composition for a volume hologram recording material according to any one of the first to fourth aspects.
As a sixth aspect, the present invention relates to a volume hologram recording medium including the volume hologram recording layer according to the fifth aspect.
As a seventh aspect, the present invention relates to the volume hologram recording medium according to the sixth aspect, wherein the volume hologram recording layer has a structure in which each of the volume hologram recording layers has a plane and is disposed between two transparent substrates facing each other.
As an eighth aspect, a step of applying the composition for a volume hologram recording material according to any one of the first to fourth aspects to a support to form a coating film, and pattern-exposing the coating film. The present invention relates to a pattern forming method including a step.
As a ninth aspect, the present invention relates to the pattern forming method according to the eighth aspect, wherein the pattern exposure is interference exposure.
　本発明によれば、微粒子として、凝集性が低く極めて高い屈折率を有するトリアジン環含有ハイパーブランチポリマーを（メタ）アクリル酸ヒドロキシアルキルとともにその他の重合性化合物などの重合性成分中に分散させることにより、光散乱損失が低く、回折効率の高いホログラムを永続的に形成できる体積ホログラム記録材料用組成物、及び体積ホログラム記録媒体を提供することができる。 According to the present invention, by dispersing triazine ring-containing hyperbranched polymer having low cohesiveness and an extremely high refractive index together with hydroxyalkyl (meth) acrylate as fine particles in a polymerizable component such as another polymerizable compound. Further, it is possible to provide a composition for a volume hologram recording material and a volume hologram recording medium capable of permanently forming a hologram having low light scattering loss and high diffraction efficiency.
図１は、製造例１で得られたＨＢ－ＴｍＤＡの１Ｈ　ＮＭＲスペクトルを示す図である。FIG. 1 is a diagram showing a 1 H NMR spectrum of HB-TmDA obtained in Production Example 1. 図２は、実施例で使用した体積ホログラム記録装置（記録／再生波長５３２ｎｍ）である。FIG. 2 shows the volume hologram recording device (recording / reproducing wavelength 532 nm) used in the example. 図３は、実施例１の体積ホログラム記録媒体（（ａ）成分：４ＨＢＡ、ＨＢ－ＴｍＤＡの体積分率：１９．６体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 3 shows the refractive index modulation with respect to the exposure time (sec) obtained using the volume hologram recording medium of Example 1 (component (a): 4HBA, volume fraction of HB-TmDA: 19.6% by volume). It is a figure which shows the change of quantity (DELTA) n. 図４は、比較例１の体積ホログラム記録媒体（（ａ）成分：ＴＨＦＡ＋ＮＶＰ、ＨＢ－ＴｍＤＡの体積分率：１９．９体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 4 shows the refractive index modulation with respect to the exposure time (sec) obtained using the volume hologram recording medium of Comparative Example 1 (component (a): THFA + NVP, volume fraction of HB-TmDA: 19.9% by volume). It is a figure which shows the change of quantity (DELTA) n. 図５は、実施例２の体積ホログラム記録媒体（ＨＢ－ＴｍＤＡの体積分率：１５．１体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 5 is a diagram showing a change in the refractive index modulation amount Δn with respect to the exposure time (second), obtained by using the volume hologram recording medium of Example 2 (volume fraction of HB-TmDA: 15.1% by volume). It is. 図６は、実施例３の体積ホログラム記録媒体（ＨＢ－ＴｍＤＡの体積分率：２０．０体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 6 is a diagram showing a change in the refractive index modulation amount Δn with respect to the exposure time (second), obtained using the volume hologram recording medium of Example 3 (volume fraction of HB-TmDA: 20.0 vol%). It is. 図７は、実施例４の体積ホログラム記録媒体（ＨＢ－ＴｍＤＡの体積分率：２３．０体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 7 is a diagram showing a change in the refractive index modulation amount Δn with respect to the exposure time (second), obtained using the volume hologram recording medium of Example 4 (volume fraction of HB-TmDA: 23.0% by volume). It is. 図８は、実施例５の体積ホログラム記録媒体（ＨＢ－ＴｍＤＡの体積分率：２５．０体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 8 is a diagram showing a change in the refractive index modulation amount Δn with respect to the exposure time (second) obtained using the volume hologram recording medium of Example 5 (volume fraction of HB-TmDA: 25.0% by volume). It is. 図９は、実施例で使用した体積ホログラム記録装置（記録／再生波長６４０ｎｍ）である。FIG. 9 shows a volume hologram recording device (recording / reproducing wavelength: 640 nm) used in the example. 図１０は、実施例６の体積ホログラム記録媒体（ＨＢ－ＴｍＤＡの体積分率：２０．１体積％）を用いて得られた、露光時間（秒）に対する屈折率変調量Δｎの変化を示す図である。FIG. 10 is a diagram showing a change in the refractive index modulation amount Δn with respect to the exposure time (second) obtained using the volume hologram recording medium of Example 6 (volume fraction of HB-TmDA: 20.1% by volume). It is.
　本発明の体積ホログラム記録材料用組成物は、（ａ）（メタ）アクリル酸ヒドロキシアルキル、（ｂ）（ａ）成分とは異なる重合性化合物、（ｃ）トリアジン環含有ハイパーブランチポリマー及び（ｄ）光重合開始剤を含みて構成される。
　以下、本発明の体積ホログラム記録材料用組成物に含まれる各成分について説明する。 The composition for a volume hologram recording material of the present invention comprises (a) hydroxyalkyl (meth) acrylate, (b) a polymerizable compound different from the component (a), (c) a triazine ring-containing hyperbranched polymer, and (d) It is configured to include a photopolymerization initiator.
Hereinafter, each component contained in the composition for a volume hologram recording material of the present invention will be described.
［（ａ）（メタ）アクリル酸ヒドロキシアルキル］
　本発明における（ａ）（メタ）アクリル酸ヒドロキシアルキルは、後述する（ｃ）トリアジン環含有ハイパーブランチポリマーを分散させることができ、そして後述する（ｂ）（ａ）成分とは異なる重合性化合物に対して、（ｃ）成分とともに分散し得る成分として機能する。
　なお本明細書において（メタ）アクリル酸とはメタクリル酸とアクリル酸の双方を表す。 [(A) Hydroxyalkyl (meth) acrylate]
The (a) hydroxyalkyl (meth) acrylate in the present invention can disperse the (c) triazine ring-containing hyperbranched polymer described below, and can be used as a polymerizable compound different from the (b) (a) component described later. On the other hand, it functions as a component that can be dispersed together with the component (c).
In this specification, (meth) acrylic acid represents both methacrylic acid and acrylic acid.
　上記（ａ）成分は、（メタ）アクリル酸アルキルエステル化合物において、該化合物のアルキル基が少なくとも１つのヒドロキシ基で置換された化合物であれば特に限定されず、該アルキル基が２以上のヒドロキシ基で置換された化合物であってもよく、また、さらにその他の置換基にて置換された化合物であってもよい。
　中でも（ａ）成分として、アルキル基がヒドロキシ基以外に置換基を持たない（ヒドロキシ基のみでアルキル基が置換されている）（メタ）アクリル酸ヒドロキシアルキルを好適に使用でき、例えばアルキル基が１つのヒドロキシ基のみで置換された（メタ）アクリル酸モノヒドロキシアルキルを使用できる。 The component (a) is not particularly limited as long as it is a compound in which the alkyl group of the (meth) acrylic acid alkyl ester compound is substituted with at least one hydroxy group, and the alkyl group has two or more hydroxy groups. Or a compound further substituted with another substituent.
Among them, as the component (a), a hydroxyalkyl (meth) acrylate in which the alkyl group has no substituent other than the hydroxy group (the alkyl group is substituted only by the hydroxy group) can be preferably used. Monohydroxyalkyl (meth) acrylates substituted with only one hydroxy group can be used.
　上記（ａ）成分として、例えば炭素原子数１～２０のヒドロキシアルキル基を有する（メタ）アクリル酸エステル化合物が挙げられる。
　炭素原子数１～２０のヒドロキシアルキル基としては、例えば、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシヘキシル基、ヒドロキシヘプチル基、ヒドロキシオクチル基、ヒドロキシノニル基、ヒドロキシデシル基、ヒドロキシウンデシル基、ヒドロキシドデシル基、ヒドロキシトリデシル基、ヒドロキシテトラデシル基、ヒドロキシペンタデシル基、ヒドロキシヘキサデシル基、ヒドロキシヘプタデシル基、ヒドロキシオクタデシル基、ヒドロキシノナデシル基及びヒドロキシエイコシル基が挙げられる。これらヒドロキシアルキル基は直鎖状、分枝鎖状、環状、あるいはそれらの組合せのいずれであってもよい。 Examples of the component (a) include (meth) acrylate compounds having a hydroxyalkyl group having 1 to 20 carbon atoms.
Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group , Hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl and hydroxyeico And a sil group. These hydroxyalkyl groups may be linear, branched, cyclic, or a combination thereof.
　上記（ａ）成分の具体例を挙げると、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシ－１－メチルエチル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシヘプチル、（メタ）アクリル酸ヒドロキシオクチル、（メタ）アクリル酸ヒドロキシノニル、（メタ）アクリル酸ヒドロキシデシル、（メタ）アクリル酸３－ヒドロキシアダマンチル、（メタ）アクリル酸ヒドロキシウンデシル、（メタ）アクリル酸ヒドロキシドデシル（（メタ）アクリル酸ヒドロキシラウリルという場合もある。）、（メタ）アクリル酸ヒドロキシトリデシル、（メタ）アクリル酸ヒドロキシテトラデシル、（メタ）アクリル酸ヒドロキシペンタデシル、（メタ）アクリル酸ヒドロキシヘキサデシル、（メタ）アクリル酸ヒドロキシヘプタデシル、（メタ）アクリル酸ヒドロキシオクタデシル、（メタ）アクリル酸ヒドロキシノナデシル、（メタ）アクリル酸ヒドロキシエイコシル、グリセリンモノ（メタ）アクリレート、１，１，１－トリメチロールプロパンモノ（メタ）アクリレート、ペンタエリスリトールモノ（メタ）アクリレート等が挙げられる。これらは、単独で又は２種以上を組み合わせて用いられる。
　これらの中でも、後述する（ｃ）成分の分散性及び（ｂ）成分への分散性を考慮すると、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシ－１－メチルエチル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシヘプチル、（メタ）アクリル酸ヒドロキシオクチル、（メタ）アクリル酸ヒドロキシノニル、（メタ）アクリル酸ヒドロキシデシル、（メタ）アクリル酸ヒドロキシウンデシル又は（メタ）アクリル酸ヒドロキシドデシルを用いることができる。
　特に、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシ－１－メチルエチル、（メタ）アクリル酸４－ヒドロキシブチルが好ましく、（メタ）アクリル酸４－ヒドロキシブチルがより好ましい。 Specific examples of the component (a) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-1 (meth) acrylate. -Methylethyl, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, (meth) acryl Hydroxynonyl acid, hydroxydecyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, hydroxyundecyl (meth) acrylate, hydroxydodecyl (meth) acrylate (or hydroxylauryl (meth) acrylate) .), (Meth) acrylic Hydroxytridecyl, hydroxytetradecyl (meth) acrylate, hydroxypentadecyl (meth) acrylate, hydroxyhexadecyl (meth) acrylate, hydroxyheptadecyl (meth) acrylate, hydroxyoctadecyl (meth) acrylate, (meth) ) Hydroxynonadecyl acrylate, hydroxyeicosyl (meth) acrylate, glycerin mono (meth) acrylate, 1,1,1-trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and the like. These are used alone or in combination of two or more.
Among these, considering the dispersibility of the component (c) and the dispersibility in the component (b) described later, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acryl 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxy (meth) acrylate Octyl, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate or hydroxydodecyl (meth) acrylate can be used.
In particular, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1-methylethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable. ) 4-Hydroxybutyl acrylate is more preferred.
　本発明の体積ホログラム記録材料用組成物における（ａ）（メタ）アクリル酸ヒドロキシアルキルの配合量は、（ｂ）（ａ）成分とは異なる重合性化合物１質量部に対し０．１～１，０００質量部、好ましくは０．５～５００質量部、より好ましくは１～５００質量部、例えば１～１００質量部である。 In the composition for a volume hologram recording material of the present invention, the compounding amount of (a) hydroxyalkyl (meth) acrylate is 0.1 to 1, based on 1 part by mass of a polymerizable compound different from the component (b) and (a). 000 parts by mass, preferably 0.5 to 500 parts by mass, more preferably 1 to 500 parts by mass, for example 1 to 100 parts by mass.
［（ｂ）（ａ）成分とは異なる重合性化合物］
　本発明における（ｂ）成分の重合性化合物は、光重合開始剤の作用によって重合する重合性の部位を、分子内に１個以上、好ましくは１乃至６個有する化合物であり、（ａ）成分：（メタ）アクリル酸ヒドロキシアルキルとは異なる化合物であれば特に制限はない。重合性の部位としては、ラジカル重合性の部位であるエチレン性不飽和結合が挙げられる。
　なお、本発明における重合性化合物とは、いわゆる反応性を有しない高分子物質ではない化合物を意味し、従って、狭義の単量体化合物（モノマー）だけでなく、二量体、三量体、オリゴマーや反応性高分子をも包含するものである。 [(B) a polymerizable compound different from the component (a)]
The polymerizable compound of the component (b) in the present invention is a compound having one or more, preferably 1 to 6 polymerizable sites in the molecule, which is polymerized by the action of a photopolymerization initiator. : There is no particular limitation as long as it is a compound different from hydroxyalkyl (meth) acrylate. Examples of the polymerizable site include an ethylenically unsaturated bond that is a radical polymerizable site.
In addition, the polymerizable compound in the present invention means a compound that is not a so-called non-reactive polymer substance, and therefore includes not only a monomer compound (monomer) in a narrow sense, but also a dimer, a trimer, It also includes oligomers and reactive polymers.
　このような重合性化合物としては、ラジカル重合性の部位又はカチオン重合性の部位を有する化合物が挙げられる。
　ラジカル重合性の部位を有する重合性化合物としては、エチレン性不飽和結合を有する化合物が挙げられる。また、カチオン重合性の部位を有する重合性化合物としては、ビニルチオエーテル構造、或いは、エポキシ環又はオキセタン環などの環状エーテル構造を有する化合物が挙げられる。 Examples of such a polymerizable compound include a compound having a radically polymerizable site or a cationically polymerizable site.
Examples of the polymerizable compound having a radical polymerizable site include a compound having an ethylenically unsaturated bond. Examples of the polymerizable compound having a cationically polymerizable site include a compound having a vinyl thioether structure or a cyclic ether structure such as an epoxy ring or an oxetane ring.
＜ラジカル重合性の部位を有する重合性化合物＞
　エチレン性不飽和結合を有する化合物としては、例えば、不飽和カルボン酸；不飽和カルボン酸エステル化合物；脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と不飽和カルボン酸及び多価カルボン酸とのエステル化反応により得られるエステル化合物等；並びにこれらのアルキレンオキシド変性物（エチレンオキシド変性物、プロピレンオキシド変性物等）が挙げられる。 <Polymerizable compound having radical polymerizable site>
Examples of the compound having an ethylenically unsaturated bond include: unsaturated carboxylic acid; unsaturated carboxylic acid ester compound; ester compound of aliphatic polyhydroxy compound and unsaturated carboxylic acid; aromatic polyhydroxy compound and unsaturated carboxylic acid An ester compound obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polyvalent carboxylic acid; and an alkylene oxide-modified product thereof. (Modified products of ethylene oxide, propylene oxide, etc.).
　不飽和カルボン酸の具体例としては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸等が挙げられる。 Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.
　不飽和カルボン酸エステル化合物の具体例としては、フェノキシエチレングリコールアクリレート、フェノキシジエチレングリコールアクリレート、２－アクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、イソボロニルアクリレート等のアクリル酸エステル化合物が挙げられる。また、これらの例示化合物のアクリレート部分をメタクリレートに代えたメタクリル酸エステル化合物、同様にイタコネートに代えたイタコン酸エステル化合物、クロトネートに代えたクロトン酸エステル化合物、及びマレエートに代えたマイレン酸エステル化合物等も挙げられる。 Specific examples of the unsaturated carboxylic acid ester compound include acrylic acid ester compounds such as phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and isobornyl acrylate. . In addition, methacrylic acid ester compounds in which the acrylate moiety of these exemplified compounds is replaced with methacrylate, itaconic acid ester compounds similarly replaced with itaconate, crotonic acid ester compounds replaced with crotonate, and maleic acid ester compounds replaced with maleate are also included. No.
　脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物の具体例としては、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールポリアクリレート等のアクリル酸エステル化合物が挙げられる。また、これらの例示化合物のアクリレート部分をメタクリレートに代えたメタクリル酸エステル化合物、同様にイタコネートに代えたイタコン酸エステル化合物、クロトネートに代えたクロトン酸エステル化合物、マレエートに代えたマイレン酸エステル化合物等も挙げられる。 Specific examples of the ester compound of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol Acrylic ester compounds such as triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol polyacrylate are exemplified. In addition, methacrylic acid ester compounds in which the acrylate portion of these exemplified compounds is replaced with methacrylate, itaconic acid ester compounds similarly replaced with itaconate, crotonic acid ester compounds replaced with crotonate, maleic acid ester compounds replaced with maleate, etc. Can be
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物としては、ヒドロキノンジアクリレート、ヒドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等が挙げられる。 Examples of the ester compound of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
　脂肪族ポリヒドロキシ化合物及び芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と不飽和カルボン酸及び多価カルボン酸とのエステル化反応により得られるエステル化合物としては、必ずしも単一物では無いが、代表的な具体例を挙げれば、アクリル酸及びフタル酸とエチレングリコールとの縮合物、アクリル酸及びマレイン酸とジエチレングリコールとの縮合物、メタクリル酸及びテレフタル酸とペンタエリスリトールとの縮合物、アクリル酸及びアジピン酸とブタンジオール及びグリセリンとの縮合物等が挙げられる。 As an ester compound obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polyvalent carboxylic acid, the ester compound is not necessarily a single substance, but is typically used. Specific examples include condensates of acrylic acid and phthalic acid with ethylene glycol, condensates of acrylic acid and maleic acid with diethylene glycol, condensates of methacrylic acid and terephthalic acid with pentaerythritol, acrylic acid and adipic acid And butanediol and glycerin.
　以上のエステル化合物以外に、エチレン性不飽和結合を有する化合物として、多価イソシアネートとヒドロキシアルキル不飽和カルボン酸エステルとの反応によって得ることができるウレタン化合物や、多価エポキシ化合物とヒドロキシアルキル不飽和カルボン酸エステルとの反応によって得ることができる化合物を挙げることができる。上記ウレタン化合物の例としては、例えばダイセル・サイテック（株）製ＥＢＥＣＲＹＬ（登録商標）シリーズウレタンアクリレートが挙げられ、具体的には、例えばＥＢＥＣＲＹＬ８３０１などを使用することによって、分散性を損なうことなく優れた回折効率を得ることができる。
　その他本発明に用いられるエチレン性不飽和結合を有する化合物の例としては、フタル酸ジアリル等のアリルエステル化合物；ジビニルフタレート等のビニル基含有化合物等が有用である。 In addition to the above ester compounds, as compounds having an ethylenically unsaturated bond, urethane compounds that can be obtained by reacting a polyvalent isocyanate with a hydroxyalkyl unsaturated carboxylic acid ester, or a polyvalent epoxy compound and a hydroxyalkyl unsaturated carboxylic acid Examples include compounds that can be obtained by reaction with an acid ester. Examples of the urethane compound include, for example, EBECRYL (registered trademark) series urethane acrylate manufactured by Daicel Cytec Co., Ltd. Specifically, for example, by using EBECRYL8301, etc., excellent dispersibility is obtained without impairing dispersibility. Diffraction efficiency can be obtained.
Other examples of the compound having an ethylenically unsaturated bond used in the present invention include an allyl ester compound such as diallyl phthalate; and a vinyl group-containing compound such as divinyl phthalate.
　本発明においては、エチレン性不飽和結合を有する化合物として、アクリル酸エステル化合物及びメタクリル酸エステル化合物、並びにそれらのアルキレンオキシド変性物（エチレンオキシド変性物、プロピレンオキシド変性物等）を特に好ましく用いることができる。中でも、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物である多官能（メタ）アクリル酸エステル化合物、並びにそれらのアルキレンオキシド変性物（エチレンオキシド変性物、プロピレンオキシド変性物等）を好適例として挙げることができる。
　これらのエチレン性不飽和結合を有する化合物は単独で用いてもよいし、必要に応じ混合して用いてもよい。 In the present invention, as the compound having an ethylenically unsaturated bond, an acrylate compound and a methacrylate compound, and their alkylene oxide modified products (ethylene oxide modified product, propylene oxide modified product, etc.) can be particularly preferably used. . Among them, preferred are polyfunctional (meth) acrylate compounds, which are ester compounds of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and alkylene oxide-modified products thereof (ethylene oxide-modified products, propylene oxide-modified products, etc.). Can be mentioned.
These compounds having an ethylenically unsaturated bond may be used alone, or may be used as a mixture if necessary.
＜カチオン重合性の部位を有する重合性化合物＞
　エポキシ環を有する化合物としては、例えば、ジグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、１，４－ビス（２，３－エポキシプロポキシパーフルオロイソプロピル）シクロヘキサン、ソルビトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レゾルシンジグリシジルエーテル、１，６－へキサンジオールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、フェニルグリシジルエーテル、ｐ－ｔｅｒｔ－ブチルフェニルグリシジルエーテル、アジピン酸ジグリシジルエステル、ｏ－フタル酸ジグリシジルエステル、ジブロモフェニルグリシジルエーテル、１，２，７，８－ジエポキシオクタン、１，６－ジメチロールパーフルオロヘキサンジグリシジルエーテル、４，４’－ビス（２，３－エポキシプロポキシパーフルオロイソプロピル）ジフェニルエーテル、２，２－ビス（４－グリシジルオキシフェニル）プロパン、３，４－エポキシシクロヘキシルメチル３’，４’－エポキシシクロヘキサンカルボキシレート、３，４－エポキシシクロヘキシルオキシラン、２－（３，４－エポキシシクロヘキシル）－３’，４’－エポキシ－１，３－ジオキサン－５－スピロシクロヘキサン、１，２－エチレンジオキシビス（３，４－エポキシシクロヘキシルメタン）、４’，５’－エポキシ－２’－メチルシクロヘキシルメチル４，５－エポキシ－２－メチルシクロヘキサンカルボキシレート、エチレングリコールビス（３，４－エポキシシクロヘキサンカルボキシレート）、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ジ－２，３－エポキシシクロペンチルエーテル等を挙げることができる。 <Polymerizable compound having cationically polymerizable site>
Examples of the compound having an epoxy ring include diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, and trimethylolpropane polyglycidyl. Ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester , Dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexanedi Ricidyl ether, 4,4'-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl 3 ', 4'- Epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2- (3,4-epoxycyclohexyl) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy Bis (3,4-epoxycyclohexylmethane), 4 ', 5'-epoxy-2'-methylcyclohexylmethyl 4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol bis (3,4-epoxycyclohexanecarboxylate) ), Bis (3,4-epoki) (Cyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether and the like.
　オキセタン環を有する化合物としては、例えば、３－エチル－３－ヒドロキシメチルオキセタン、３－エチル－３－（フェノキシメチル）オキセタン、３，３－ジエチルオキセタン、３－エチル－３－（２－エチルヘキシルオキシメチル）オキセタン等のオキセタン環を１つ有する化合物；１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、ジ（３－エチル－３－オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３－エチル－３－オキセタニルメチル）エーテル等のオキセタン環を２つ以上有する化合物を挙げることができる。 Examples of the compound having an oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3,3-diethyloxetane, and 3-ethyl-3- (2-ethylhexyloxy Compounds having one oxetane ring such as methyl) oxetane; 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol Examples thereof include compounds having two or more oxetane rings such as tetrakis (3-ethyl-3-oxetanylmethyl) ether.
　これらのカチオン重合性の部位を有する重合性化合物は単独で用いてもよいし、必要に応じ混合して用いてもよい。 重合 These polymerizable compounds having a cationically polymerizable site may be used alone, or may be used as a mixture if necessary.
＜重合性化合物＞
　本発明において、（ｂ）成分：（ａ）成分とは異なる重合性化合物は、一種を単独で用いてもよく、二種以上を組合せて用いてもよい。
　また、（ｂ）成分として、重合性の部位を１個有する化合物と、重合性の部位を２個以上有する化合物を（２官能以上の重合性化合物）を併用してもよい。重合性の部位を１個有する化合物と２個以上有する化合物との併用により、後述する（ｃ）トリアジン環含有ハイパーブランチポリマーの拡散が速やかに起こり、回折効率などの特性がさらに好ましい形態となることが期待される。
　なお、（ｂ）成分として２官能以上の重合性化合物を使用する場合、その使用量（質量）は、組成物の合計質量から２官能以上の重合性化合物を除いた質量に対して１０倍量（質量）までが好適とされる。２官能以上の重合性化合物の使用量がこの割合以上に多くなると、（ｃ）トリアジン環含有ハイパーブランチポリマーの分散量が相対的に少なくなり、回折効率などにおいてよい特性が得られない場合がある点に留意する。
　上記２官能以上の重合性化合物としては前出のラジカル重合性の部位を有する重合性化合物或いはカチオン重合性化合物を有する化合物において、重合性の部位を２個以上有する化合物が挙げられる。
　また、上記（ｂ）（ａ）成分とは異なる重合性化合物として、特に多官能（メタ）アクリレート、並びにそれらのアルキレンオキシド変性物を用いることが好適である。 <Polymerizable compound>
In the present invention, the polymerizable compound different from the component (b): component (a) may be used alone or in combination of two or more.
As the component (b), a compound having one polymerizable site and a compound having two or more polymerizable sites (bifunctional or more polymerizable compound) may be used in combination. By using a compound having one polymerizable site and a compound having two or more polymerizable sites, the diffusion of the (c) triazine ring-containing hyperbranched polymer described later occurs promptly, and characteristics such as diffraction efficiency become more preferable. There is expected.
When a bifunctional or higher functional polymerizable compound is used as the component (b), the amount (mass) used is 10 times the mass of the total mass of the composition excluding the bifunctional or higher functional polymerizable compound. (Mass) is preferred. When the amount of the bifunctional or higher functional polymerizable compound is more than this ratio, the dispersion amount of (c) the triazine ring-containing hyperbranched polymer becomes relatively small, and good characteristics such as diffraction efficiency may not be obtained in some cases. Note the points.
Examples of the bifunctional or higher functional polymerizable compound include the compounds having two or more polymerizable sites in the above-mentioned compounds having a radical polymerizable site or compounds having a cationic polymerizable compound.
As the polymerizable compound different from the components (b) and (a), it is particularly preferable to use a polyfunctional (meth) acrylate and an alkylene oxide-modified product thereof.
［（ｃ）トリアジン環含有ハイパーブランチポリマー］
　本発明の体積ホログラム記録材料用組成物は、（ｃ）トリアジン環含有ハイパーブランチポリマーを必須の成分として含む。
　本発明の体積ホログラム記録材料用組成物に含まれる上記（ｃ）成分の配合量は、前記（ａ）成分、前記（ｂ）成分、及び（ｃ）成分の合計体積に占める（ｃ）成分の割合として、３体積％以上、５０体積％以下であることが好ましく、より好ましくは１５体積％以上５０体積％以下である。 [(C) Triazine ring-containing hyperbranched polymer]
The composition for a volume hologram recording material of the present invention contains (c) a triazine ring-containing hyperbranched polymer as an essential component.
The amount of the component (c) contained in the composition for a volume hologram recording material of the present invention is such that the component (c) accounts for the total volume of the component (a), the component (b), and the component (c). The ratio is preferably 3% by volume or more and 50% by volume or less, more preferably 15% by volume or more and 50% by volume or less.
　トリアジン環含有ハイパーブランチポリマーとしては、下記式（１）で表される繰り返し単位構造を含むポリマーが好ましい。
Figure JPOXMLDOC01-appb-C000001
 上記式（１）中、Ｒ及びＲ’は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、又はアラルキル基を表す。 As the triazine ring-containing hyperbranched polymer, a polymer containing a repeating unit structure represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000001
 In the above formula (1), R and R ′ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
　本発明において、アルキル基の炭素原子数は特に限定されるものではないが、炭素原子数が１～２０であることが好ましく、重合体の耐熱性をより高めることを考慮すると、炭素原子数１～１０であることがより好ましく、１～３であることがより一層好ましい。また、その構造は、直鎖状、分岐鎖状、環状のいずれでもよい。
　アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、シクロブチル基、１－メチルシクロプロピル基、２－メチルシクロプロピル基、ｎ－ペンチル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１，１－ジメチルプロピル基、１，２－ジメチルプロピル基、２，２－ジメチルプロピル基、１－エチルプロピル基、シクロペンチル基、１－メチルシクロブチル基、２－メチルシクロブチル基、３－メチルシクロブチル基、１，２－ジメチルシクロプロピル基、２，３－ジメチルシクロプロピル基、１－エチルシクロプロピル基、２－エチルシクロプロピル基、ｎ－ヘキシル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１，１－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、２，２－ジメチルブチル基、２，３－ジメチルブチル基、３，３－ジメチルブチル基、１－エチルブチル基、２－エチルブチル基、１，１，２－トリメチルプロピル基、１，２，２－トリメチルプロピル基、１－エチル－１－メチルプロピル基、１－エチル－２－メチルプロピル基、シクロヘキシル基、１－メチルシクロペンチル基、２－メチルシクロペンチル基、３－メチルシクロペンチル基、１－エチルシクロブチル基、２－エチルシクロブチル基、３－エチルシクロブチル基、１，２－ジメチルシクロブチル基、１，３－ジメチルシクロブチル基、２，２－ジメチルシクロブチル基、２，３－ジメチルシクロブチル基、２，４－ジメチルシクロブチル基、３，３－ジメチルシクロブチル基、１－プロピルシクロプロピル基、２－プロピルシクロプロピル基、１－イソプロピルシクロプロピル基、２－イソプロピルシクロプロピル基、１，２，２－トリメチルシクロプロピル基、１，２，３－トリメチルシクロプロピル基、２，２，３－トリメチルシクロプロピル基、１－エチル－２－メチルシクロプロピル基、２－エチル－１－メチルシクロプロピル基、２－エチル－２－メチルシクロプロピル基、２－エチル－３－メチルシクロプロピル基等が挙げられる。 In the present invention, the number of carbon atoms in the alkyl group is not particularly limited. However, the number of carbon atoms is preferably from 1 to 20, and in consideration of further increasing the heat resistance of the polymer, the number of carbon atoms is preferably 1 to 20. It is more preferably from 10 to 1, and still more preferably from 1 to 3. Further, the structure may be linear, branched or cyclic.
Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl Cyclopropyl group, 2-methylcyclopropyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2 -Dimethylpropyl, 1-ethylpropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclo Propyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methylpe Butyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethyl Butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -Ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethylcyclobutyl group, 2-ethyl Cyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethyl Cyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-propylcyclopropyl, 2-propylcyclopropyl, 1-isopropylcyclopropyl , 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl Group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group and the like.
　上記アルコキシ基の炭素原子数は特に限定されるものではないが、炭素原子数が１～２０であることが好ましく、重合体の耐熱性をより高めることを考慮すると、炭素原子数１～１０であることがより好ましく、１～３であることがより一層好ましい。また、そのアルキル部分の構造は、直鎖状、分岐鎖状、環状のいずれでもよい。
　アルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ｎ－ペンチルオキシ基、１－メチルブトキシ基、２－メチルブトキシ基、３－メチルブトキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、２，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ｎ－ヘキシルオキシ基、１－メチルペンチルオキシ基、２－メチルペンチルオキシ基、３－メチルペンチルオキシ基、４－メチルペンチルオキシ基、１，１－ジメチルブトキシ基、１，２－ジメチルブトキシ基、１，３－ジメチルブトキシ基、２，２－ジメチルブトキシ基、２，３－ジメチルブトキシ基、３，３－ジメチルブトキシ基、１－エチルブトキシ基、２－エチルブトキシ基、１，１，２－トリメチルプロポキシ基、１，２，２－トリメチルプロポキシ基、１－エチル－１－メチルプロポキシ基、１－エチル－２－メチルプロポキシ基等が挙げられる。 The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms, and is preferably 1 to 10 carbon atoms in consideration of further increasing the heat resistance of the polymer. More preferably, it is more preferably 1-3. The structure of the alkyl moiety may be linear, branched or cyclic.
Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 1-methyl Butoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexyloxy , 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethyl Butoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy 1-ethylbutoxy group, 2-ethylbutoxy group, 1,1,2-trimethylpropoxy group, 1,2,2-trimethylpropoxy group, 1-ethyl-1-methylpropoxy group, 1-ethyl-2-methylpropoxy And the like.
　上記アリール基の炭素原子数は特に限定されるものではないが、炭素原子数が６～４０であることが好ましく、重合体の耐熱性をより高めることを考慮すると、炭素原子数６～１６であることがより好ましく、６～１３であることがより一層好ましい。
　アリール基の具体例としては、フェニル基、ｏ－クロルフェニル基、ｍ－クロルフェニル基、ｐ－クロルフェニル基、ｏ－フルオロフェニル基、ｐ－フルオロフェニル基、ｏ－メトキシフェニル基、ｐ－メトキシフェニル基、ｐ－ニトロフェニル基、ｐ－シアノフェニル基、α－ナフチル基、β－ナフチル基、ｏ－ビフェニリル基、ｍ－ビフェニリル基、ｐ－ビフェニリル基、１－アントリル基、２－アントリル基、９－アントリル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、４－フェナントリル基、９－フェナントリル基等が挙げられる。 Although the number of carbon atoms of the aryl group is not particularly limited, it is preferably 6 to 40 carbon atoms. In consideration of further increasing the heat resistance of the polymer, the aryl group has 6 to 16 carbon atoms. More preferably, it is more preferably 6 to 13.
Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxy Phenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, Examples thereof include a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.
　アラルキル基の炭素原子数は特に限定されるものではないが、炭素原子数が７～２０であることが好ましく、そのアルキル部分は、直鎖状、分岐鎖状、環状のいずれでもよい。
　その具体例としては、ベンジル基、ｐ－メチルフェニルメチル基、ｍ－メチルフェニルメチル基、ｏ－エチルフェニルメチル基、ｍ－エチルフェニルメチル基、ｐ－エチルフェニルメチル基、２－プロピルフェニルメチル基、４－イソプロピルフェニルメチル基、４－イソブチルフェニルメチル基、α－ナフチルメチル基等が挙げられる。 The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched, or cyclic.
Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl And 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, α-naphthylmethyl and the like.
　上記式（１）中、Ａｒは、下記式（２）乃至式（１３）で表される群から選ばれる少なくとも１種の二価の基を表す。
Figure JPOXMLDOC01-appb-C000002
 In the above formula (1), Ar represents at least one divalent group selected from the group represented by the following formulas (2) to (13).
Figure JPOXMLDOC01-appb-C000002
　上記式（２）乃至式（１３）中、Ｒ１～Ｒ９２は、互いに独立して、水素原子、ハロゲン原子、カルボキシ基、スルホ基、炭素原子数１～１０の分岐構造を有していてもよいアルキル基、又は炭素原子数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｒ９３及びＲ９４は、水素原子又は炭素原子数１～１０の分岐構造を有していてもよいアルキル基を表し、Ｗ１及びＷ２は、互いに独立して、単結合、ＣＲ９５Ｒ９６（式中、Ｒ９５及びＲ９６は、互いに独立して、水素原子又は炭素原子数１～１０の分岐構造を有していてもよいアルキル基（ただし、Ｒ９５とＲ９６は結合する炭素原子と一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ２、又はＮＲ９７（式中、Ｒ９７は、水素原子又は炭素原子数１～１０の分岐構造を有していてもよいアルキル基を表す。）を表す。
　これらアルキル基、アルコキシ基としては上記において挙げた基と同様の基が挙げられる。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 In the above formulas (2) to (13), R 1 to R 92 each independently have a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, or a branched structure having 1 to 10 carbon atoms. Represents an alkyl group or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms, and R 93 and R 94 each have a hydrogen atom or a branched structure having 1 to 10 carbon atoms. And W 1 and W 2 are each independently a single bond, CR 95 R 96 (wherein R 95 and R 96 are each independently a hydrogen atom or a carbon atom having 1 carbon atom. And an alkyl group which may have a branched structure of up to 10 (provided that R 95 and R 96 may form a ring together with the carbon atoms to which they are bonded), and C ＝ O , O, S, SO, SO 2, or NR 97 (wherein, R 97 is It represents a represents.) A hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms.
Examples of the alkyl group and the alkoxy group include the same groups as those described above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　また上記式中、Ｘ１及びＸ２は、互いに独立して、単結合、炭素原子数１～１０の分岐構造を有していてもよいアルキレン基、又は式（１４）
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ９８～Ｒ１０１は、互いに独立して、水素原子、ハロゲン原子、カルボキシ基、スルホ基、炭素原子数１～１０の分岐構造を有していてもよいアルキル基、又は炭素原子数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ１及びＹ２は、互いに独立して、単結合又は炭素原子数１～１０の分岐構造を有していてもよいアルキレン基を表す。）
で表される基を表す。
　これらハロゲン原子、アルキル基、アルコキシ基としては上記において挙げた基と同様の基が挙げられる。
　また炭素原子数１～１０の分岐構造を有していてもよいアルキレン基としては、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基等が挙げられる。 In the above formula, X 1 and X 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a compound represented by the formula (14)
Figure JPOXMLDOC01-appb-C000003
 (Wherein, R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom Represents an alkoxy group which may have a branched structure having 1 to 10 carbon atoms, and Y 1 and Y 2 may each independently have a single bond or a branched structure having 1 to 10 carbon atoms. Represents an alkylene group.)
Represents a group represented by
Examples of the halogen atom, alkyl group and alkoxy group include the same groups as those described above.
Examples of the alkylene group which may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and the like.
　本発明における前記式（１）における好適なＡｒとしては、式（２）、（５）乃至（１３）で表される基から選ばれる少なくとも１種が挙げられ、式（２）、（５）、（７）、（８）、（１１）乃至（１３）で表される基から選ばれる少なくとも１種がより好ましい。 Suitable Ar in the formula (1) in the present invention includes at least one selected from the groups represented by the formulas (2) and (5) to (13), and the formulas (2) and (5) , (7), (8), and at least one selected from the groups represented by (11) to (13).
　上記式（２）乃至式（１３）で表されるアリール基（Ａｒ）の具体例としては、下記式で示されるものが挙げられるが、これらに限定されるものではない。 具体 Specific examples of the aryl group (Ar) represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulas.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　これらの中でも、より高い屈折率を発現するハイパーブランチポリマーが得られることから、下記式で示されるアリール基がより好ましい。 中 で も Among these, an aryl group represented by the following formula is more preferable because a hyperbranched polymer that expresses a higher refractive index can be obtained.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　中でも、（ｃ）トリアジン環含有ハイパーブランチポリマーに含まれる好適な繰り返し単位構造としては、式（１）で表される繰り返し単位構造において、Ａｒが式（２）で表される二価の基であるもの、すなわち、下記式（１５）で示される繰り返し単位構造が好ましい。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ、Ｒ’及びＲ１～Ｒ４は、前記と同じ意味を表す。） Among them, (c) a preferred repeating unit structure contained in the triazine ring-containing hyperbranched polymer is a repeating unit structure represented by the formula (1), wherein Ar is a divalent group represented by the formula (2). Certain of them, that is, a repeating unit structure represented by the following formula (15) is preferable.
Figure JPOXMLDOC01-appb-C000006
 (In the formula, R, R ′ and R 1 to R 4 represent the same meaning as described above.)
　そして特に好適な繰り返し単位構造としては、下記式（１６）で表される繰り返し単位構造が挙げられ、中でも下記式（１７）で表される繰り返し単位構造を含むトリアジン環含有ハイパーブランチポリマーが最適である。 As a particularly preferred repeating unit structure, a repeating unit structure represented by the following formula (16) can be mentioned, and among them, a triazine ring-containing hyperbranched polymer containing a repeating unit structure represented by the following formula (17) is most suitable. is there.
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ及びＲ’は、上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000007
 (In the formula, R and R ′ represent the same meaning as described above.)
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　本発明における（ｃ）トリアジン環含有ハイパーブランチポリマーの重量平均分子量は特に限定されるものではないが、５００～５００，０００が好ましく、さらに５００～１００，０００が好ましく、より耐熱性を向上させるとともに、収縮率を低くするという点から、２，０００以上が好ましく、より溶解性を高め、得られた溶液の粘度を低下させるという点から、５０，０００以下が好ましく、３０，０００以下がより好ましく、さらに１０，０００以下が好ましい。
　なお、本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下、ＧＰＣという）分析による標準ポリスチレン換算で得られる平均分子量である。 The weight average molecular weight of the triazine ring-containing hyperbranched polymer (c) in the present invention is not particularly limited, but is preferably from 500 to 500,000, more preferably from 500 to 100,000. In view of lowering the shrinkage, 2,000 or more is preferable, and 50,000 or less is preferable, and 30,000 or less is more preferable, from the viewpoint of increasing the solubility and lowering the viscosity of the obtained solution. And more preferably 10,000 or less.
In addition, the weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter, referred to as GPC) analysis in terms of standard polystyrene.
　上記（ｃ）トリアジン環含有ハイパーブランチポリマーは、国際公開第２０１０／１２８６６１号パンフレットに開示された手法によって製造することができる。その一例を挙げるとすれば、例えば、下記スキーム１に示されるように、ハロゲン化シアヌル（１８）及びｍ－フェニレンジアミン化合物（１９）を適当な有機溶媒中で反応させることにより繰り返し単位構造（１７’）を有するトリアジン環含有ハイパーブランチポリマーを得ることができる。 The triazine ring-containing hyperbranched polymer (c) can be produced by the method disclosed in WO 2010/128661. For example, as shown in the following Scheme 1, a repeating unit structure (17) is obtained by reacting a cyanuric halide (18) and an m-phenylenediamine compound (19) in an appropriate organic solvent. ') A triazine ring-containing hyperbranched polymer having ()) can be obtained.
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｘは、互いに独立してハロゲン原子を表す。Ｒは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000009
 (In the formula, X independently represents a halogen atom. R represents the same meaning as described above.)
［（ｄ）光重合開始剤］
　本発明における光重合開始剤としては、後に詳述するパターン露光によって前記（ａ）成分及び／又は前記（ｂ）成分：（ａ）成分とは異なる重合性化合物の重合を開始することができる機能を有する化合物であれば特に限定はない。
　前記（ｂ）成分：（ａ）成分とは異なる重合性化合物としてラジカル重合性の部位であるエチレン性不飽和結合を有する化合物を使用する場合、光重合開始剤としては、基本的にはパターン露光時に活性ラジカルを生成する光ラジカル重合開始剤が用いられる。
　また、前記（ｂ）成分：（ａ）成分とは異なる重合性化合物としてカチオン重合性の部位であるビニルエーテル構造、エポキシ環又はオキセタン環を有する化合物等を使用する場合、光重合開始剤としては、基本的にはパターン露光時にルイス酸あるいはブレンステッド酸を生成する光酸発生剤が用いられる。 [(D) Photopolymerization initiator]
As the photopolymerization initiator in the present invention, a function capable of initiating polymerization of a polymerizable compound different from the component (a) and / or the component (b) by the pattern exposure described in detail below. There is no particular limitation as long as the compound has
Component (b): When a compound having an ethylenically unsaturated bond, which is a radical polymerizable site, is used as a polymerizable compound different from component (a), the photopolymerization initiator is basically a pattern exposure. A photo-radical polymerization initiator that sometimes generates an active radical is used.
Component (b): When a compound having a vinyl ether structure, an epoxy ring, or an oxetane ring, which is a cationically polymerizable site, is used as the polymerizable compound different from the component (a), the photopolymerization initiator may be: Basically, a photoacid generator that generates a Lewis acid or Bronsted acid during pattern exposure is used.
＜光ラジカル重合開始剤＞
　光ラジカル重合開始剤としては、パターン露光時に活性ラジカルを生成する化合物であれば特に限定されないが、例えば、ベンゾイン系化合物、α－アミノアルキルフェノン系化合物、Ｎ－アリール－α－アミノ酸系化合物、チオキサントン系化合物、アゾ系化合物、アジド系化合物、ジアゾ系化合物、ｏ－キノンジアジド系化合物、アシルホスフィンオキシド系化合物、オキシムエステル系化合物、有機過酸化物、ベンゾフェノン類、ビスクマリン、ビスイミダゾール化合物、チタノセン化合物、チオール化合物、ハロゲン化炭化水素化合物、トリクロロメチルトリアジン系化合物、ホウ素化合物、あるいはヨードニウム塩化合物、スルホニウム塩化合物などのオニウム塩化合物等が用いられる。光ラジカル重合開始剤は単独で用いてもよいし、必要に応じて二種以上を混合して用いてもよい。 <Photo-radical polymerization initiator>
The photo-radical polymerization initiator is not particularly limited as long as it is a compound that generates an active radical at the time of pattern exposure. Examples thereof include a benzoin compound, an α-aminoalkylphenone compound, an N-aryl-α-amino acid compound, and thioxanthone. Compounds, azo compounds, azide compounds, diazo compounds, o-quinonediazide compounds, acylphosphine oxide compounds, oxime ester compounds, organic peroxides, benzophenones, biscoumarins, bisimidazole compounds, titanocene compounds, A thiol compound, a halogenated hydrocarbon compound, a trichloromethyltriazine-based compound, a boron compound, or an onium salt compound such as an iodonium salt compound or a sulfonium salt compound is used. The photoradical polymerization initiator may be used alone, or may be used as a mixture of two or more as needed.
　チタノセン化合物としては、特に限定はされないが、例えばビス（シクロペンタジエニル）ジクロロチタニウム、ビス（シクロペンタジエニル）ジフェニルチタニウム、ビス（シクロペンタジエニル）ビス（２，３，４，５，６－ペンタフルオロフェニル）チタニウム、ビス（シクロペンタジエニル）ビス（２，３，５，６－テトラフルオロフェニル）チタニウム、ビス（シクロペンタジエニル）ビス（２，４，６－トリフルオロフェニル）チタニウム、ビス（シクロペンタジエニル）ビス（２，６－ジフルオロフェニル）チタニウム、ビス（シクロペンタジエニル）ビス（２，４－ジフルオロフェニル）チタニウム、ビス（メチルシクロペンタジエニル）ビス（２，３，４，５，６－ペンタフルオロフェニル）チタニウム、ビス（メチルシクロペンタジエニル）ビス（２，３，５，６－テトラフルオロフェニル）チタニウム、ビス（２，６－ジフルオロフェニル）ビス（メチルシクロペンタジエニル）チタニウム、ビス（シクロペンタジエニル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウム等を挙げることができる。 The titanocene compound is not particularly limited. For example, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) bis (2,3,4,5,6) -Pentafluorophenyl) titanium, bis (cyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4,6-trifluorophenyl) titanium , Bis (cyclopentadienyl) bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3 , 4,5,6-pentafluorophenyl) titanium, bis (methyl) Clopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (2,6-difluorophenyl) bis (methylcyclopentadienyl) titanium, bis (cyclopentadienyl) bis (2 , 6-Difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
　Ｎ－アリール－α－アミノ酸系化合物としては、特に限定はされないが、例えばＮ－フェニルグリシン、Ｎ－（ｐ－メチルフェニル）グリシン、Ｎ－（ｐ－アセチルフェニル）グリシン、Ｎ－（ｍ－アセチルフェニル）グリシン、Ｎ－（ｐ－トリフルオロメチルフェニル）グリシン、Ｎ－（ｍ－トリフルオロメチルフェニル）グリシン、Ｎ－（ｐ－メトキシフェニル）グリシン、Ｎ－（ｍ－メトキシフェニル）グリシン、Ｎ－（ｐ－メトキシカルボニルフェニル）グリシン、Ｎ－（ｍ－クロロフェニル）グリシン、Ｎ－（ｏ－クロロフェニル）グリシン、Ｎ－（ｐ－フルオロフェニル）グリシン、Ｎ－（ｐ－シアノフェニル）グリシン、Ｎ－（ｍ－シアノフェニル）グリシン、Ｎ－メチル－Ｎ－フェニルグリシン、Ｎ－エチル－Ｎ－フェニルグリシン、Ｎ－フェニルアラニン、Ｎ－（ｐ－アセチルフェニル）アラニン、Ｎ－（ｍ－アセチルフェニル）アラニン等を挙げることができる。 The N-aryl-α-amino acid-based compound is not particularly limited. For example, N-phenylglycine, N- (p-methylphenyl) glycine, N- (p-acetylphenyl) glycine, N- (m-acetyl) Phenyl) glycine, N- (p-trifluoromethylphenyl) glycine, N- (m-trifluoromethylphenyl) glycine, N- (p-methoxyphenyl) glycine, N- (m-methoxyphenyl) glycine, N- (P-methoxycarbonylphenyl) glycine, N- (m-chlorophenyl) glycine, N- (o-chlorophenyl) glycine, N- (p-fluorophenyl) glycine, N- (p-cyanophenyl) glycine, N- ( m-cyanophenyl) glycine, N-methyl-N-phenylglycine, N-ethyl-N-phenyl Glycine, N- phenylalanine, N- (p-acetylphenyl) alanine, mention may be made of N-(m-acetylphenyl) alanine or the like.
　トリクロロメチルトリアジン系化合物としては、特に限定はされないが、例えば２，４，６－トリス（トリクロロメチル）－１，３，５－トリアジン、２，４，６－トリス（トリブロモメチル）－１，３，５－トリアジン、２，４，６－トリス（ジクロロメチル）－１，３，５－トリアジン、２，４，６－トリス（ジブロモメチル）－１，３，５－トリアジン、２，４，６－トリス（クロロメチル）－１，３，５－トリアジン、２，４，６－トリス（ブロモメチル）－１，３，５－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン、２－メチル－４，６－ビス（トリブロモメチル）－１，３，５－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン、２－フェニル－４，６－ビス（トリブロモメチル）－１，３，５－トリアジン、２－（ｐ－クロロフェニル）－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン等を挙げることができる。 The trichloromethyltriazine-based compound is not particularly limited. For example, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl) -1, 3,5-triazine, 2,4,6-tris (dichloromethyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2,4 6-tris (chloromethyl) -1,3,5-triazine, 2,4,6-tris (bromomethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1 , 3,5-Triazine, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5- Triazine, 2-Fe 4,6-bis (tribromomethyl) -1,3,5-triazine and 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine Can be.
　ベンゾイン系化合物としては、例えばベンゾインエチルエーテル、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン等を挙げることができる。 Examples of the benzoin-based compound include benzoin ethyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON etc. can be mentioned.
　α－アミノアルキルフェノン系化合物としては、例えば２－メチル－１－（４－（メチルチオ）フェニル）－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン等を挙げることができる。 Examples of the α-aminoalkylphenone-based compound include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butan-1-one and the like.
　チオキサントン系化合物としては、例えばチオキサントン、１－クロロチオキサントン、２－クロロチオキサントン、１－クロロ－４－プロポキシチオキサントン、２－メチルチオキサントン、２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン等を挙げることができる。 Examples of thioxanthone compounds include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethyl Thioxanthone and the like can be mentioned.
　アゾ系化合物としては、２，２’－アゾビス（２－アミジノプロパン）塩酸塩、４，４’－アゾビス（４－シアノ吉草酸）、２，２’－アゾビス（Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン）、ジメチル２，２’－アゾビスイソブチレート、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス（２－メチル－Ｎ－（２－（１－ヒドロキシブチル））プロピオンアミド）、２，２’－アゾビス（２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド）、２，２’－アゾビス（２－（５－メチル－２－イミダゾリン－２－イル）プロパン）塩酸塩、２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）塩酸塩、２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）硫酸塩、２，２’－アゾビス（２－（３，４，５，６－テトラヒドロピリミジン－２－イル）プロパン）塩酸塩、２，２’－アゾビス（２－（１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル）プロパン）塩酸塩、２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）等を挙げることができる。 Examples of the azo compound include 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), and 2,2′-azobis (N- (2-carboxyethyl) -2-methylpropionamidine), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methyl-N- (2- (1-hydroxybutyl)) ) Propionamide), 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), 2,2′-azobis (2- (5-methyl-2-imidazoline-2-i) ) Propane) hydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl) propane) hydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl) propane) sulfuric acid Salt, 2,2′-azobis (2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane) hydrochloride, 2,2′-azobis (2- (1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane) hydrochloride, 2,2'-azobis (2- (2-imidazolin-2-yl) propane) and the like.
　アジド系化合物としては、例えばｐ－アジドベンズアルデヒド、ｐ－アジドアセトフェノン、ｐ－アジド安息香酸、ｐ－アジドベンザルアセトフェノン、４，４’－ジアジドカルコン、４，４’－ジアジドジフェニルスルフィド、２，６－ビス（４’－アジドベンザル）－４－メチルシクロヘキサノン、４，４’－ジアジドスチルベン等を挙げることができる。 Examples of the azide compound include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidediphenyl sulfide, , 6-bis (4'-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidostilbene and the like.
　ジアゾ系化合物としては、例えば２，５－ジエトキシ－４－ｐ－トリルメルカプトベンゼンジアゾニウムテトラフルオロボレート、４－（ジメチルアミノ）ベンゼンジアゾニウムクロリド、４－（ジエチルアミノ）ベンゼンジアゾニウムテトラフルオロボレート等を挙げることができる。 Examples of the diazo compound include 2,5-diethoxy-4-p-tolylmercaptobenzenediazonium tetrafluoroborate, 4- (dimethylamino) benzenediazonium chloride, and 4- (diethylamino) benzenediazonium tetrafluoroborate. it can.
　ｏ－キノンジアジド系化合物としては、例えば１，２－ナフトキノンジアジド（２）－４－スルホン酸ナトリウム塩、１，２－ナフトキノンジアジド（２）－５－スルホン酸エステル、１，２－ナフトキノンジアジド（２）－４－スルホニルクロリド等を挙げることができる。 Examples of the o-quinonediazide compound include 1,2-naphthoquinonediazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester, and 1,2-naphthoquinonediazide (2 ) -4-sulfonyl chloride and the like.
　アシルホスフィンオキシド系化合物としては、例えばフェニルビス（２，４，６－トリメチルベンゾイル）ホスフィンオキシド、ジフェニル（２，４，６－トリメチルベンゾイル）ホスフィンオキシド等を挙げることができる。 Examples of the acylphosphine oxide compounds include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.
　オキシムエステル系化合物としては、例えば２－（Ｏ－ベンゾイルオキシム）－１－（４－（フェニルチオ）フェニル）－１，２－オクタンジオン、１－（Ｏ－アセチルオキシム）－１－（９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル）エタノン等を挙げることが出来る。 Examples of the oxime ester compounds include 2- (O-benzoyloxime) -1- (4- (phenylthio) phenyl) -1,2-octanedione and 1- (O-acetyloxime) -1- (9-ethyl And -6- (2-methylbenzoyl) -9H-carbazol-3-yl) ethanone.
　ベンゾフェノン類としては、例えばベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、１，４－ジベンゾイルベンゼン、１０－ブチル－２－クロロアクリドン、２－ベンゾイルナフタレン、４－ベンゾイルビフェニル、４－ベンゾイルジフェニルエーテル、３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノン等を挙げることができる。 Examples of benzophenones include benzophenone, 4,4'-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, and 4-benzoyl Examples thereof include diphenyl ether and 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone.
　ビスクマリンとしては、例えば３，３’－カルボニルビス（７－ジエチルアミノクマリン）等が挙げられ、これはみどり化学株式会社でＢＣ（ＣＡＳ［６３２２６－１３－１］）として市販されている。 Biscoumarin includes, for example, 3,3'-carbonylbis (7-diethylaminocoumarin), which is commercially available as BC (CAS [63226-13-1]) from Midori Kagaku.
　ビスイミダゾール化合物としては、例えば２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラキス（３，４，５－トリメトキシフェニル）－１，２’－ビイミダゾール、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール等を挙げることができる。 Examples of the bisimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) -1,2′-biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.
　ホウ素化合物としては、特に限定はされないが、例えば、トリエチルホウ素、トリプロピルホウ素、トリブチルホウ素、トリヘキシルホウ素、トリシクロヘキシルホウ素等のトリアルキルホウ素類；トリフェニルホウ素、トリナフチルホウ素等のトリアリールホウ素類；エトキシジエチルホウ素、プロポキシジプロピルホウ素、ブトキシジブチルホウ素などのアルコキシジアルキルホウ素類；及び、アルキルトリアリールボレート（ブチルトリフェニルボレート、ブチルトリナフチルボレート等）、ジアルキルジアリールボレート（ジブチルジフェニルボレート、ジブチルジナフチルボレート等）、トリアルキルアリールボレート（トリブチルフェニルボレート、トリブチルナフチルボレート等）などのボレートの、金属塩（リチウム、ナトリウム、カリウム、マグネシウム等）、アンモニウム塩（テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム等）、ピリジニウム塩（メチルピリジニウム、エチルピリジニウム、ブチルピリジニウム等）、キノリニウム塩（メチルキノリニウム、エチルキノリニウム、ブチルキノリニウム等）、ホスホニウム塩、スルホニウム塩等が挙げられる。 Examples of the boron compound include, but are not particularly limited to, trialkyl borons such as triethyl boron, tripropyl boron, tributyl boron, trihexyl boron, and tricyclohexyl boron; and triaryl borons such as triphenyl boron and trinaphthyl boron. Alkoxydialkylborons such as ethoxydiethylboron, propoxydipropylboron and butoxydibutylboron; and alkyltriarylborates (such as butyltriphenylborate and butyltrinaphthylborate); and dialkyldiarylborates (dibutyldiphenylborate and dibutyldinaphthyl). Borates such as trialkylaryl borates (such as tributyl phenyl borate and tributyl naphthyl borate). Lithium, potassium, magnesium, etc.), ammonium salts (tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.), pyridinium salts (methylpyridinium, ethylpyridinium, butylpyridinium, etc.), quinolinium salts (methylquinolinium, ethylquinolinium) Butylquinolinium), phosphonium salts, sulfonium salts and the like.
　なお、これら光ラジカル重合開始剤のうち、チタノセン化合物、Ｎ－アリール－α－アミノ酸系化合物、及びトリクロロメチルトリアジン系化合物が好ましい。また、チタノセン化合物の中でもビス（シクロペンタジエニル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウムを、Ｎ－アリール－α－アミノ酸系化合物の中でもＮ－フェニルグリシンを、トリクロロメチルトリアジン系化合物の中でも２，４，６－トリス（トリクロロメチル）－１，３，５－トリアジンを好適例として挙げることができる。なおＮ－フェニルグリシンは、後述するローズベンガル、３，３’－ジプロピルチアジカルボシアニンヨージド等の増感剤と組合せて用いてもよく、２，４，６－トリス（トリクロロメチル）－１，３，５－トリアジンは、後述する３，３’－ジプロピルチアジカルボシアニンヨージド等の増感剤と組合せて用いてもよい。 チ Among these radical photopolymerization initiators, titanocene compounds, N-aryl-α-amino acid compounds, and trichloromethyltriazine compounds are preferred. Among the titanocene compounds, bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium is replaced with N-aryl-α-amino acid-based compound. Preferred examples of phenylglycine include 2,4,6-tris (trichloromethyl) -1,3,5-triazine among trichloromethyltriazine-based compounds. N-phenylglycine may be used in combination with a sensitizer such as rose bengal or 3,3′-dipropylthiazicarbocyanine iodide described later, and 2,4,6-tris (trichloromethyl)- 1,3,5-Triazine may be used in combination with a sensitizer such as 3,3'-dipropylthiazicarbocyanine iodide described below.
＜光酸発生剤＞
　光酸発生剤としては、パターン露光時にルイス酸あるいはブレンステッド酸を生成する化合物であれば特に限定されないが、例えば、ジアリールヨードニウム塩化合物、トリアリールスルホニウム塩化合物、ジアゾニウム塩化合物などのオニウム塩化合物、鉄アレーン錯体化合物等を挙げることができる。 <Photoacid generator>
The photoacid generator is not particularly limited as long as it is a compound that generates a Lewis acid or a Bronsted acid at the time of pattern exposure.For example, diaryliodonium salt compounds, triarylsulfonium salt compounds, onium salt compounds such as diazonium salt compounds, Iron arene complex compounds and the like can be mentioned.
　ジアリールヨードニウム塩化合物としては、例えば、ジフェニルヨードニウム、４，４’－ジクロロジフェニルヨードニウム、４，４’－ジメトキシジフェニルヨードニウム、４，４’－ジ－ｔｅｒｔ－ブチルジフェニルヨードニウム、（４－メチルフェニル）（４－（２－メチルプロピル）フェニル）ヨードニウム、３，３’－ジニトロフェニルヨードニウム等のヨードニウムの、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、ヘキサフルオロアンチモネート等が挙げられる。 Examples of the diaryliodonium salt compound include diphenyliodonium, 4,4'-dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tert-butyldiphenyliodonium, (4-methylphenyl) ( Examples of iodonium such as 4- (2-methylpropyl) phenyl) iodonium and 3,3′-dinitrophenyliodonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
　トリアリールスルホニウム塩化合物としては、例えば、トリフェニルスルホニウム、ジフェニル（４－ｔｅｒｔ－ブチルフェニル）スルホニウム、トリス（４－メチルフェニル）スルホニウム、トリス（４－メトキシフェニル）スルホニウム、ジフェニル（４－フェニルチオフェニル）スルホニウム等のスルホニウムの、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、ヘキサフルオロアンチモネート等を挙げることができる。 Examples of the triarylsulfonium salt compound include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, and diphenyl (4-phenylthiophenyl) ) Examples of sulfonium such as sulfonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
　鉄アレーン錯体化合物としては、例えばビスシクロペンタジエニル－（η６－イソプロピルベンゼン）－鉄（ＩＩ）ヘキサフルオロホスフェート等が挙げられる。 Examples of the iron arene complex compound include biscyclopentadienyl- (η 6 -isopropylbenzene) -iron (II) hexafluorophosphate.
　これら光ラジカル重合開始剤、光酸発生剤などの光重合開始剤は単独で用いてもよいし、必要に応じて二種以上を混合して用いてもよい。
　本発明の体積ホログラム記録材料用組成物における光重合開始剤の配合量は、前記（ａ）成分、及び前記（ｂ）成分：（ａ）成分とは異なる重合性化合物の総量に対し０．０１～１０質量％であり、好ましくは０．０５～５質量％である。 These photopolymerization initiators such as the photoradical polymerization initiator and the photoacid generator may be used alone, or may be used as a mixture of two or more as needed.
The blending amount of the photopolymerization initiator in the composition for a volume hologram recording material of the present invention is 0.01 to the total amount of the component (a) and the component (b): the total amount of the polymerizable compound different from the component (a). To 10% by mass, preferably 0.05 to 5% by mass.
［体積ホログラム記録媒体］
　本発明は上記（ａ）乃至（ｄ）成分を含有する体積ホログラム記録材料用組成物を含む体積ホログラム記録層並びに該記録層を含む体積ホログラム記録媒体も対象とする。
　本発明の体積ホログラム記録媒体における記録層には、上記（ａ）乃至（ｄ）成分の他、必要に応じて、増感剤、連鎖移動剤、可塑剤、着色剤等の添加剤を加えてもよい。 [Volume hologram recording medium]
The present invention is also directed to a volume hologram recording layer containing the composition for a volume hologram recording material containing the components (a) to (d), and a volume hologram recording medium containing the recording layer.
The recording layer of the volume hologram recording medium of the present invention may contain, if necessary, additives such as a sensitizer, a chain transfer agent, a plasticizer, and a coloring agent in addition to the components (a) to (d). Is also good.
　例えば、増感剤は前記光重合開始剤の光に対する感度を増加させるために用いることができる。増感剤としては、例えば、２，６－ジエチル－１，３，５，７，８－ペンタメチルピロメテン－ＢＦ２錯体、１，３，５，７，８－ペンタメチルピロメテン－ＢＦ２錯体等のピロメテン錯体化合物；エオシン、エチルエオシン、エリスロシン、フルオレセイン、ローズベンガル等のキサンテン系色素；３，３’－ジエチルオキサカルボシアニンヨージド、３，３’－ジエチルチアカルボシアニンヨージド、３，３’－ジエチルオキサジカルボシアニンヨージド、３，３’－ジプロピルチアジカルボシアニンヨージド、３，３，３’，３’－テトラメチル－１，１’－ビス（４－スルホブチル）ベンゾインドジカルボシアニンナトリウム等のシアニン色素；２，４－ビス［４－（ジエチルアミノ）－２－ヒドロキシフェニル］スクアライン、２，４－ビス［８－ヒドロキシ－１，１，７，７－テトラメチルジュロリジン－９－イル］スクアライン等のスクアリウム色素；１－（１－メチルナフト〔１，２－ｄ〕チアゾール－２（１Ｈ）－イリデン）－４－（２，３，６，７－テトラヒドロ－１Ｈ，５Ｈ－ベンゾ〔ｉｊ〕キノリジン－９－イル）－３－ブテン－２－オン、１－（３－メチルベンゾチアゾール－２（３Ｈ）－イリデン）－４－（ｐ－ジメチルアミノフェニル）－３－ブテン－２－オン等のケトチアゾリン化合物；２－（ｐ－ジメチルアミノスチリル）－ナフト〔１，２－ｄ〕チアゾール、２－（４－（ｐ－ジメチルアミノフェニル）－１，３－ブタジエニル）ナフト〔１，２－ｄ〕チアゾール等のスチリル又はフェニルブタジエニル複素環化合物などが挙げられる。また、２，４－ジフェニル－６－（ｐ－ジメチルアミノスチリル）－１，３，５－トリアジン、２，４－ジフェニル－６－（（２，３，６，７－テトラヒドロ－１Ｈ，５Ｈ－ベンゾ〔ｉｊ〕キノリジン－９－イル）－１－エテン－２－イル）－１，３，５－トリアゾンナンスリル＝（２，３，６，７－テトラヒドロ－１Ｈ，５Ｈ－ベンゾ〔ｉｊ〕キノリジン－９－イル）－１－エテン－２－イル＝ケトン、２，５－ビス（ｐ－ジメチルアミノシンナミリデン）シクロペンタノン、５，１０，１５，２０－テトラフェニルポルフィリン等が挙げられる。増感剤が使用される場合、その添加量としては、前記（ｄ）光重合開始剤１質量部に対して、例えば、０．０１～２０質量部、好ましくは０．０１～１０質量部である。 For example, a sensitizer can be used to increase the sensitivity of the photopolymerization initiator to light. Examples of the sensitizer include 2,6-diethyl-1,3,5,7,8-pentamethylpyrromethene-BF 2 complex and 1,3,5,7,8-pentamethylpyrromethene-BF 2 Pyrromethene complex compounds such as complexes; xanthene dyes such as eosin, ethyl eosin, erythrosine, fluorescein, and rose bengal; 3,3′-diethyloxacarbocyanine iodide, 3,3′-diethylthiacarbocyanine iodide; 3′-diethyloxadicarbocyanine iodide, 3,3′-dipropylthiazicarbocyanine iodide, 3,3,3 ′, 3′-tetramethyl-1,1′-bis (4-sulfobutyl) benzoin Cyanine dyes such as sodium dodicarbocyanine; 2,4-bis [4- (diethylamino) -2-hydroxyphenyl] squaraine, 2,4-bi Squarium dyes such as [8-hydroxy-1,1,7,7-tetramethyljulolidin-9-yl] squaraine; 1- (1-methylnaphtho [1,2-d] thiazole-2 (1H) -ylidene ) -4- (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolinidin-9-yl) -3-buten-2-one, 1- (3-methylbenzothiazole-2 (3H ) -Ylidene) -4- (p-dimethylaminophenyl) -3-buten-2-one and other ketothiazoline compounds; 2- (p-dimethylaminostyryl) -naphtho [1,2-d] thiazole, 2- ( Examples include styryl or phenylbutadienyl heterocyclic compounds such as 4- (p-dimethylaminophenyl) -1,3-butadienyl) naphtho [1,2-d] thiazole. Further, 2,4-diphenyl-6- (p-dimethylaminostyryl) -1,3,5-triazine, 2,4-diphenyl-6-((2,3,6,7-tetrahydro-1H, 5H- Benzo [ij] quinolizin-9-yl) -1-ethen-2-yl) -1,3,5-triazonanthryl = (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] Quinolizin-9-yl) -1-ethen-2-yl = ketone, 2,5-bis (p-dimethylaminocinnamylidene) cyclopentanone, 5,10,15,20-tetraphenylporphyrin and the like . When a sensitizer is used, it is added in an amount of, for example, 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 1 part by mass of the photopolymerization initiator (d). is there.
　また、膜厚の均一性を持たせ、光照射での重合で形成された干渉膜を安定に存在させるためには結合材としてバインダ樹脂を加えてもよい。
　バインダ樹脂は前記樹脂成分（（ａ）及び（ｂ）成分）と相溶性のよいものが好ましく、その具体例としては塩素化ポリエチレン、ポリメチル（メタ）アクリレート、メチル（メタ）アクリレートと他の（メタ）アクリル酸アルキルエステルの共重合体、塩化ビニルとアクリロニトリルの共重合体、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルピロリドン、エチルセルロース、アセチルセルロースなどが挙げられる。 In addition, a binder resin may be added as a binder in order to have a uniform film thickness and stably exist an interference film formed by polymerization by light irradiation.
The binder resin preferably has good compatibility with the resin components (components (a) and (b)), and specific examples thereof include chlorinated polyethylene, polymethyl (meth) acrylate, methyl (meth) acrylate, and other (meth) acrylates. ) Copolymers of acrylic acid alkyl esters, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, acetyl cellulose and the like.
　本発明の体積ホログラム記録用組成物を用いて体積ホログラム記録層並びに体積ホログラム記録媒体を作るには（ａ）乃至（ｄ）成分を、必要に応じ、増感剤、及びバインダ樹脂等とともに混合し、このまま無溶剤で透明基体（支持体）上に塗布するか、これらの混合物に溶剤又は添加剤を加えて所謂ワニスの形態とし、これを透明基体上に塗布、乾燥して、透明基体上に体積ホログラム記録層が形成した記録媒体を得る。
　さらに該記録層上に透明基体、或いは酸素遮断のための保護層を設け、体積ホログラム記録層が２枚の透明基体間、或いは透明基体と保護層間に配置された構造とすることもできる。 In order to produce a volume hologram recording layer and a volume hologram recording medium using the composition for volume hologram recording of the present invention, the components (a) to (d) are mixed with a sensitizer, a binder resin and the like, if necessary. It is applied as it is on a transparent substrate (support) without solvent, or a mixture of these is added with a solvent or an additive to form a so-called varnish, which is coated on the transparent substrate and dried to form a varnish on the transparent substrate. A recording medium on which a volume hologram recording layer is formed is obtained.
Further, a transparent substrate or a protective layer for blocking oxygen may be provided on the recording layer, and the volume hologram recording layer may be arranged between two transparent substrates or between the transparent substrate and the protective layer.
　上記溶剤としては、使用成分に対して十分な溶解度を持ち、良好な塗膜性を与えるものであれば特に制限はないが、例えば、メチルセロソルブ、エチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート等のセロソルブ系溶剤；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル等のプロピレングリコール系溶剤；酢酸ブチル、酢酸アミル、酢酸エチル、酢酸ブチル、ジエチルオキサレート、ピルビン酸エチル、２－ヒドロキシ酪酸エチル、アセト酢酸エチル、乳酸メチル、乳酸エチル、３－メトキシプロピオン酸メチル等のエステル系溶剤；ブタノール、ヘプタノール、ヘキサノール、ジアセトンアルコール、フルフリルアルコール等のアルコール系溶剤；メチルイソブチルケトン、シクロヘキサノン、メチルアミルケトン等のケトン系溶剤；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド系溶剤；あるいはこれらの混合溶剤、さらには、これらに芳香族炭化水素を添加したもの等が挙げられる。
　上記溶剤を使用する場合、その使用量の割合は、本実施形態の体積ホログラム用材料組成物の総量に対して、通常、質量比で１～２０倍程度の範囲である。 The solvent is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties.For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve solvents; propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; Butyl acetate, amyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl pyruvate, 2-hydroxy Ester solvents such as ethyl acetate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate; alcohol solvents such as butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; methyl isobutyl ketone, cyclohexanone; Ketone solvents such as methyl amyl ketone; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; or a mixed solvent thereof, Those to which hydrogen has been added can be given.
When the solvent is used, the amount of the solvent is usually in the range of about 1 to 20 times by mass relative to the total amount of the volume hologram material composition of the present embodiment.
　上記透明基体としては、透明なガラス板、アクリル板、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム等が用いられる。塗布方法としては、従来公知の方法、例えば、回転塗布、ワイヤーバー塗布、ディップ塗布、エアーナイフ塗布、ロール塗布、ブレード塗布、及びカーテン塗布等を用いることができる。 透明 As the transparent substrate, a transparent glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene film or the like is used. As a coating method, a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, or the like can be used.
　上記保護層としては、酸素による感度低下や保存安定性の劣化等の悪影響を防止するための公知技術、例えば、水溶性ポリマー等の塗布を用いることもできる。 As the protective layer, a known technique for preventing adverse effects such as a decrease in sensitivity and a deterioration in storage stability due to oxygen, for example, a coating of a water-soluble polymer or the like can be used.
　本発明はまた、前記体積ホログラム記録材料用組成物を用いるパターン形成方法も対象とする。
　すなわち、前記体積ホログラム記録材料用組成物を、支持体に塗布し塗布膜を形成する工程、及び前記塗布膜にパターン露光する工程を含む方法であって、特に前記パターン露光が干渉露光であることが好ましい。
　上記支持体としては前述の透明基体として挙げたものを好適に使用でき、また支持体への塗布方法としては前述の透明基体上への塗布方法を挙げることができる。 The present invention is also directed to a pattern forming method using the composition for a volume hologram recording material.
That is, a method including a step of applying the composition for a volume hologram recording material to a support to form a coating film, and a step of pattern-exposing the coating film, and in particular, the pattern exposure is interference exposure. Is preferred.
As the above-mentioned support, those mentioned above as the transparent substrate can be suitably used, and as the method of coating on the support, the above-mentioned method of coating on the transparent substrate can be mentioned.
　前述したとおり、体積ホログラム記録用組成物として従来、屈折率の異なる複数の官能性モノマーからなる組成物や液状有機物と官能性モノマーからなる組成物などが知られている。こうした組成物を用いて回折効率の高いホログラムを得るためには、干渉縞の明部に当たる領域と暗部に当たる領域の屈折率差を大きくする必要がある。しかしながら従来提案されている有機物の屈折率は通常１．３～１．６程度に限られることから、有機物同士の組合せからなるホログラム記録材料では屈折率差を大きくするのに限界があるとされていた。
　本発明において使用するトリアジン環含有ハイパーブランチポリマーは１．７を上回る高い屈折率を有し、このため、従来限界があるとされた有機物（樹脂成分など）との組合せにおいても屈折率差を大きく取ることができ、従って回折光率の高いホログラムを得ることができる。 As described above, as a composition for volume hologram recording, a composition composed of a plurality of functional monomers having different refractive indices, a composition composed of a liquid organic substance and a functional monomer, and the like are conventionally known. In order to obtain a hologram having high diffraction efficiency using such a composition, it is necessary to increase the difference in the refractive index between the region corresponding to the bright portion and the region corresponding to the dark portion of the interference fringes. However, the refractive index of conventionally proposed organic substances is usually limited to about 1.3 to 1.6, and it is said that there is a limit to increasing the refractive index difference in a hologram recording material composed of a combination of organic substances. Was.
The triazine ring-containing hyperbranched polymer used in the present invention has a high refractive index exceeding 1.7, and therefore has a large refractive index difference even in combination with an organic substance (such as a resin component) which has been regarded as having a limit in the past. Therefore, a hologram having a high diffracted light rate can be obtained.
　本発明の体積ホログラム記録材料用組成物を用いた体積ホログラム記録媒体における体積ホログラムの記録原理は、以下のように推察される。
　ホログラムなどのパターンは、記録層に含まれる少なくとも二種の成分の、干渉縞の明暗部への相互拡散による屈折率の差を利用して、光の干渉パターンを記録することにより形成される。従って、パターンを形成するためのパターン露光の条件下（例えばホログラム記録のための干渉露光の条件下）で、例えば本発明の場合には、上記の（メタ）アクリル酸ヒドロキシアルキルやその他の重合性化合物などの重合性成分より生じる重合体の屈折率と、トリアジン環含有ハイパーブランチポリマーの屈折率との差が大きいことが重要となる。 The principle of recording a volume hologram in a volume hologram recording medium using the composition for a volume hologram recording material of the present invention is inferred as follows.
A pattern such as a hologram is formed by recording an interference pattern of light using a difference in refractive index between at least two kinds of components included in the recording layer due to mutual diffusion of interference fringes into bright and dark portions. Therefore, under the conditions of pattern exposure for forming a pattern (for example, conditions of interference exposure for hologram recording), for example, in the case of the present invention, the above-mentioned hydroxyalkyl (meth) acrylate and other polymerizable It is important that the difference between the refractive index of a polymer formed from a polymerizable component such as a compound and the refractive index of a triazine ring-containing hyperbranched polymer is large.
　すなわち、本発明においては、ホログラム記録のための干渉露光に用いる光の波長に対して、トリアジン環含有ハイパーブランチポリマーの屈折率と、（メタ）アクリル酸ヒドロキシアルキルやその他の重合性化合物などの重合性成分より生じる重合体の屈折率との差が大きいことが好ましいといえ、例えば差が０．０１～０．６であることが好ましいといえる。さらに該屈折率の差が０．０２～０．５、又は０．０３～０．４であることがより好ましいといえる。なお一般に、（メタ）アクリレート系重合体の屈折率は１．４９～１．５３、エポキシ系重合体の屈折率は１．５５～１．６１である。そして、このような観点から、前述の成分、すなわち、本発明で用いる好適な（ｃ）トリアジン環含有ハイパーブランチポリマーと、重合性成分（特に（メタ）アクリル酸ヒドロキシアルキルとは異なる（ｂ）重合性化合物）が夫々選択されることとなる。
　なお、該トリアジン環含有ハイパーブランチポリマーの屈折率は比較的高く、例えば、波長５８９ｎｍの光に対する屈折率は１．７を超えるものがある。このため、本発明で用いられる重合性成分（（メタ）アクリル酸ヒドロキシアルキルと、それとは異なる重合性化合物）より生ずる重合体の屈折率は、上記数値と比べて相対的に小さいことが好ましく、例えば、波長５８９ｎｍの光に対する屈折率が１．３以上、１．７以下である重合体を与える重合性成分が好ましく使用される。より好ましくは波長５８９ｎｍの光に対する屈折率が１．３～１．６である重合体を与える重合性成分（重合性化合物など）が使用されることとなる。 That is, in the present invention, the refractive index of the triazine ring-containing hyperbranched polymer and the polymerization of hydroxyalkyl (meth) acrylate and other polymerizable compounds are determined with respect to the wavelength of light used for interference exposure for hologram recording. It can be said that it is preferable that the difference from the refractive index of the polymer generated from the acidic component is large. For example, it is preferable that the difference be 0.01 to 0.6. Further, it can be said that the difference in the refractive index is more preferably 0.02 to 0.5 or 0.03 to 0.4. Generally, the refractive index of the (meth) acrylate polymer is 1.49 to 1.53, and the refractive index of the epoxy polymer is 1.55 to 1.61. From such a viewpoint, the aforementioned component, that is, the (b) triazine ring-containing hyperbranched polymer suitable for use in the present invention and the polymerizable component (particularly, the (b) polymerized Compounds) are selected.
In addition, the refractive index of the triazine ring-containing hyperbranched polymer is relatively high, and for example, the refractive index with respect to light having a wavelength of 589 nm exceeds 1.7. For this reason, it is preferable that the refractive index of the polymer produced from the polymerizable component (hydroxyalkyl (meth) acrylate and a polymerizable compound different therefrom) used in the present invention is relatively smaller than the above value, For example, a polymerizable component that gives a polymer having a refractive index of 1.3 to 1.7 with respect to light having a wavelength of 589 nm is preferably used. More preferably, a polymerizable component (such as a polymerizable compound) that gives a polymer having a refractive index of 1.3 to 1.6 with respect to light having a wavelength of 589 nm is used.
　なお、重合体の屈折率は、重合性成分及び光重合開始剤からなる組成物を支持体上に塗布し、必要に応じて乾燥を行った後、ホログラム記録のための干渉露光に用いる光を用いた条件下で空間的に一様な露光を組成物に施すことによって重合体を得、その重合体の屈折率を測定することにより求めることができる。そして、このようにして得られる重合体の屈折率と、トリアジン環含有ハイパーブランチポリマーの屈折率とを基にして、本発明のホログラム記録材料用組成物に好適な重合性成分（（メタ）アクリル酸ヒドロキシアルキル及びそれとは異なる重合性化合物など）、及びトリアジン環含有ハイパーブランチポリマーをそれぞれ選択することができる。 In addition, the refractive index of the polymer, after applying a composition comprising a polymerizable component and a photopolymerization initiator on a support, drying if necessary, and then using light used for interference exposure for hologram recording. The polymer can be obtained by subjecting the composition to spatially uniform exposure under the conditions used, and can be determined by measuring the refractive index of the polymer. Then, based on the refractive index of the polymer thus obtained and the refractive index of the triazine ring-containing hyperbranched polymer, a polymerizable component ((meth) acrylic) suitable for the hologram recording material composition of the present invention is used. Hydroxyalkyl acid and a polymerizable compound different therefrom), and a triazine ring-containing hyperbranched polymer.
　以下、実施例及び比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、実施例において、試料の調製及び物性の分析に用いた装置及び条件は、以下のとおりである。
［１Ｈ　ＮＭＲ］
　装置：アジレント・テクノロジー（株）製　ＮＭＲ　Ｓｙｓｔｅｍ　４００ＮＢ
　測定溶媒：ＤＭＳＯ－ｄ６
　基準物質：テトラメチルシラン（δ０．００ｐｐｍ）
［ＧＰＣ（ゲル浸透クロマトグラフィー）］
　装置：東ソー（株）製　ＨＬＣ－８２００ＧＰＣ
　カラム：昭和電工（株）製　Ｓｈｏｄｅｘ（登録商標）　ＧＰＣ　ＫＦ－８０４Ｌ　＋　同ＫＦ－８０５Ｌ
　カラム温度：４０℃
　溶媒：ＴＨＦ
　検出器：ＵＶ（２５４ｎｍ）
　検量線：標準ポリスチレン
［膜密度］
　装置：ブルカージャパン（株）製　多目的Ｘ線回折装置　Ｄ８　ＤＩＳＣＯＶＥＲ
　管電圧－電流：５０ｋＶ－１００ｍＡ
　測定範囲：０．２－３．０００ｄｅｇ（２θ）
　ステップ幅：０．００５ｄｅｇ（２θ）
　ｔｉｍｅ／ｓｔｅｐ：０．５秒／ｓｔｅｐ
［５％重量減少温度（Ｔｄ５％）］
　装置：（株）リガク製　示差熱天秤（ＴＧ－ＤＴＡ）　ＴＧ－８１２０
　昇温速度：１０℃／分
　測定温度：２５～７５０℃
［屈折率］
　装置：ジェー・エー・ウーラム・ジャパン（株）製　高速分光エリプソメーター　Ｍ－２０００ Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the examples, the devices and conditions used for sample preparation and physical property analysis are as follows.
[ 1 H NMR]
Apparatus: NMR System 400NB manufactured by Agilent Technologies, Inc.
Measurement solvent: DMSO-d 6
Reference substance: tetramethylsilane (δ0.00ppm)
[GPC (gel permeation chromatography)]
Apparatus: Tosoh Corporation HLC-8200GPC
Column: Shodex (registered trademark) GPC KF-804L + KF-805L manufactured by Showa Denko KK
Column temperature: 40 ° C
Solvent: THF
Detector: UV (254 nm)
Calibration curve: standard polystyrene [membrane density]
Apparatus: Multipurpose X-ray diffractometer D8 DISCOVER manufactured by Bruker Japan
Tube voltage-current: 50kV-100mA
Measuring range: 0.2-3.0 deg (2θ)
Step width: 0.005 deg (2θ)
time / step: 0.5 seconds / step
[5% weight loss temperature (Td 5% )]
Apparatus: Rigaku Corporation Differential thermal balance (TG-DTA) TG-8120
Heating rate: 10 ° C / min Measurement temperature: 25-750 ° C
[Refractive index]
Apparatus: High-speed spectroscopic ellipsometer M-2000 manufactured by JA Woolam Japan Co., Ltd.
　また、用いた略号の意味は、以下のとおりである。
４ＨＢＡ：４－ヒドロキシブチルアクリレート［東京化成工業（株）製］
ＢｎＭＡ：ベンジルメタクリレート［東京化成工業（株）製］
ＭＭＡ：メチルメタクリレート［純正化学（株）製］
ＮＶＰ：Ｎ－ビニル－２－ピロリドン［純正化学（株）製］
ＴＨＦＡ：テトラヒドロフルフリルアクリレート［共栄社化学（株）製、ライトアクリレートＴＨＦ－Ａ］
ＤＰＨＡ：ジペンタエリスリトールペンタアクリレート／ジペンタエリスリトールヘキサアクリレート混合物［東亞合成（株）製、アロニックス（登録商標）Ｍ－４０３］
ＥＤＰＨＡ：エチレンオキシド変性ジペンタエリスリトールヘキサアクリレート［新中村化学工業（株）製、Ａ－ＤＰＨ－１２Ｅ］
Ｉ７８４：ビス（シクロペンタジエニル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウム［ＢＡＳＦジャパン（株）製、ＩＲＧＡＣＵＲＥ（登録商標）７８４）］
ＮＰＧ：Ｎ－フェニルグリシン［東京化成工業（株）製］
ＴＣＴ：２，４，６－トリス（トリクロロメチル）－１，３，５－トリアジン［富士フイルム和光純薬（株）製］
ＤｉＳＣ：３，３’－ジプロピルチアジカルボシアニンヨージド［東京化成工業（株）製、ＤｉＳＣ３（５）］
ＲＢ：ローズベンガル［東京化成工業（株）製］
ＤＭＡｃ：Ｎ，Ｎ－ジメチルアセトアミド
ＴＨＦ：テトラヒドロフラン The meanings of the abbreviations used are as follows.
4HBA: 4-hydroxybutyl acrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
BnMA: benzyl methacrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
MMA: methyl methacrylate [manufactured by Junsei Chemical Co., Ltd.]
NVP: N-vinyl-2-pyrrolidone [manufactured by Junsei Chemical Co., Ltd.]
THFA: Tetrahydrofurfuryl acrylate [Light acrylate THF-A, manufactured by Kyoeisha Chemical Co., Ltd.]
DPHA: dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [Aronix (registered trademark) M-403, manufactured by Toagosei Co., Ltd.]
EDPHA: ethylene oxide-modified dipentaerythritol hexaacrylate [A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.]
I784: Bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium [IRGACURE (registered trademark) 784, manufactured by BASF Japan Ltd.]
NPG: N-phenylglycine [Tokyo Chemical Industry Co., Ltd.]
TCT: 2,4,6-tris (trichloromethyl) -1,3,5-triazine [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
DiSC: 3,3′-dipropylthiadicarbocyanine iodide [DiSC 3 (5) manufactured by Tokyo Chemical Industry Co., Ltd.]
RB: Rose Bengal [Tokyo Chemical Industry Co., Ltd.]
DMAc: N, N-dimethylacetamide THF: tetrahydrofuran
［製造例１］トリアジン環含有ハイパーブランチポリマー（ＨＢ－ＴｍＤＡ）の製造
Figure JPOXMLDOC01-appb-C000010
 [Production Example 1] Production of triazine ring-containing hyperbranched polymer (HB-TmDA)
Figure JPOXMLDOC01-appb-C000010
　窒素雰囲気下、１Ｌ四口フラスコにＤＭＡｃ４５６ｇを仕込み、アセトン－ドライアイス浴により－１０℃まで冷却した。ここへ、２，４，６－トリクロロ－１，３，５－トリアジン［エボニック社製］８４．８３ｇ（０．４６０ｍｏｌ）を加え溶解させた。次に、別途ｍ－フェニレンジアミン６２．１８ｇ（０．５７５ｍｏｌ）及びアニリン１４．５７ｇ（０．１５６ｍｏｌ）をＤＭＡｃ３０４ｇに溶解させた溶液を、前記四口フラスコに滴下し、滴下終了後３０分間撹拌した。
　この反応液を、別途オイルバスにより８５℃に加熱してある２Ｌ四口フラスコ中のＤＭＡｃ６２２ｇに、送液ポンプを用いて１時間かけて滴下し、さらに１時間撹拌して重合させた。その後、アニリン１１３．９５ｇ（１．２２４ｍｏｌ）を加え、さらに１時間撹拌して反応を終了した。
　氷浴により室温（およそ２３℃）まで冷却した。ここへトリエチルアミン１１６．３６ｇ（１．１５ｍｏｌ）を滴下した後、さらに３０分間撹拌し、重合反応により副生した塩酸をクエンチした。析出した塩酸塩をろ別した。このろ液を、２８質量％アンモニア水溶液２７９．２９ｇ及びイオン交換水８，８２０ｇの混合溶液に加え、ポリマーを再沈殿させた。沈殿物をろ取し、１５０℃で８時間減圧乾燥した。得られた粗物をＴＨＦ８３３ｇに再溶解させ、イオン交換水６，６６５ｇに加え再沈殿させた。沈殿物をろ取し、１５０℃で２５時間減圧乾燥し、目的とするトリアジン環含有ハイパーブランチポリマーの微粒子［１ａ］（以下、ＨＢ－ＴｍＤＡと略す）１１８．０ｇを得た。
　得られたＨＢ－ＴｍＤＡの１Ｈ　ＮＭＲスペクトルを図１に示す。ＨＢ－ＴｍＤＡは、上記式［１ａ］で表される繰り返し単位構造を有する化合物である。ＨＢ－ＴｍＤＡのＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは４，３００、多分散度Ｍｗ／Ｍｎ（重量平均分子量／数平均分子量）は３．４、５％重量減少温度Ｔｄ５％は４１９℃であった。また膜密度測定より得られたＨＢ－ＴｍＤＡの密度は１．３２ｇ／ｃｍ３であった。
　得られたＨＢ－ＴｍＤＡの１０質量％シクロヘキサノン溶液を、ガラス基板上にスピンコート（２００ｒｐｍ×５秒間、次いで２，０００ｒｐｍ×３０秒間）し、１５０℃で１分間、次いで２５０℃で５分間加熱して塗膜を形成した。得られた塗膜の５５０ｎｍにおける屈折率は１．７９０であった。 Under a nitrogen atmosphere, 456 g of DMAc was charged into a 1 L four-necked flask, and cooled to −10 ° C. with an acetone-dry ice bath. To this, 84.83 g (0.460 mol) of 2,4,6-trichloro-1,3,5-triazine [manufactured by Evonik] was added and dissolved. Next, a solution obtained by separately dissolving 62.18 g (0.575 mol) of m-phenylenediamine and 14.57 g (0.156 mol) of aniline in 304 g of DMAc was dropped into the four-necked flask, and stirred for 30 minutes after the completion of the dropping. .
The reaction solution was added dropwise to 622 g of DMAc in a 2 L four-necked flask, which was separately heated to 85 ° C. by an oil bath, over 1 hour using a liquid sending pump, and further stirred for 1 hour to polymerize. Thereafter, 113.95 g (1.224 mol) of aniline was added, and the mixture was further stirred for 1 hour to complete the reaction.
Cooled to room temperature (approximately 23 ° C.) with an ice bath. After 116.36 g (1.15 mol) of triethylamine was added dropwise thereto, the mixture was further stirred for 30 minutes to quench hydrochloric acid by-produced by the polymerization reaction. The precipitated hydrochloride was filtered off. The filtrate was added to a mixed solution of 279.29 g of a 28% by mass aqueous ammonia solution and 8,820 g of ion-exchanged water to reprecipitate a polymer. The precipitate was collected by filtration and dried under reduced pressure at 150 ° C. for 8 hours. The obtained crude product was redissolved in 833 g of THF, added to 6,665 g of ion-exchanged water, and reprecipitated. The precipitate was collected by filtration, and dried under reduced pressure at 150 ° C. for 25 hours to obtain 118.0 g of desired triazine ring-containing hyperbranched polymer fine particles [1a] (hereinafter abbreviated as HB-TmDA).
FIG. 1 shows the 1 H NMR spectrum of the obtained HB-TmDA. HB-TmDA is a compound having a repeating unit structure represented by the above formula [1a]. The weight average molecular weight Mw measured by GPC of HB-TmDA in terms of polystyrene is 4,300, the polydispersity Mw / Mn (weight average molecular weight / number average molecular weight) is 3.4, the 5% weight loss temperature Td 5% is 419 ° C. The density of HB-TmDA obtained from the film density measurement was 1.32 g / cm 3 .
The obtained HB-TmDA 10% by mass cyclohexanone solution was spin-coated (200 rpm × 5 seconds, then 2,000 rpm × 30 seconds) on a glass substrate, and heated at 150 ° C. for 1 minute and then at 250 ° C. for 5 minutes. To form a coating film. The refractive index of the obtained coating film at 550 nm was 1.790.
［実施例１］
＜体積ホログラム記録材料用組成物の調製＞
　（ａ）（メタ）アクリル酸ヒドロキシアルキルとして、４ＨＢＡ７６４ｍｇ、（ｂ）重合性化合物として、ＤＰＨＡ３０３ｍｇ、（ｃ）トリアジン環含有ハイパーブランチポリマーとして、製造例１で得られたＨＢ－ＴｍＤＡ３２０ｍｇ、及び（ｄ）光重合開始剤として、Ｉ７８４　３．１ｍｇを混合し、５０℃で７２時間撹拌することで、体積ホログラム記録材料用組成物を調製した。
　ここで、４ＨＢＡの密度は１．０４ｇ／ｃｍ３、ＤＰＨＡの密度は１．１８６ｇ／ｃｍ３、ＨＢ－ＴｍＤＡの密度は１．３２ｇ／ｃｍ３であり、その体積はそれぞれ、４ＨＢＡ：０．７６４÷１．０４＝０．７３５ｃｍ３、ＤＰＨＡ：０．３０３÷１．１８６＝０．２５５ｃｍ３、ＨＢ－ＴｍＤＡ：０．３２÷１．３２＝０．２４２ｃｍ３であった。
　したがって、各重合性成分（４ＨＢＡ及びＤＰＨＡ）及びＨＢ－ＴｍＤＡの合計体積に占めるＨＢ－ＴｍＤＡの体積分率は、（０．２４２÷（０．７３５＋０．２５５＋０．２４２））×１００＝１９．６４、即ち１９．６体積％であった。 [Example 1]
<Preparation of composition for volume hologram recording material>
(A) 764 mg of 4HBA as hydroxyalkyl (meth) acrylate, (b) 303 mg of DPHA as a polymerizable compound, (c) 320 mg of HB-TmDA obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, and (d) As a photopolymerization initiator, 3.1 mg of I784 was mixed and stirred at 50 ° C. for 72 hours to prepare a composition for a volume hologram recording material.
Here, the density of 4HBA is 1.04 g / cm 3, the density of DPHA density of 1.186g / cm 3, HB-TmDA is 1.32 g / cm 3, respectively its volume, 4HBA: 0.764 ÷ 1.04 = 0.735 cm 3 , DPHA: 0.303 ÷ 1.186 = 0.255 cm 3 , HB-TmDA: 0.32 ÷ 1.32 = 0.242 cm 3 .
Therefore, the volume fraction of HB-TmDA in the total volume of each polymerizable component (4HBA and DPHA) and HB-TmDA is (0.242 ÷ (0.735 + 0.255 + 0.242)) × 100 = 19.64. That is, it was 19.6% by volume.
＜体積ホログラム記録媒体の作製＞
　スライドガラスの上下左右両端部に、スペーサとして厚さ１０μｍの金属箔を置き、スライドガラス中央（スペーサに挟まれた領域）に上記体積ホログラム記録材料用組成物を滴下し、体積ホログラム記録層を形成した。その後、形成した体積ホログラム記録層を挟むように別のスライドガラスを被せ、体積ホログラム記録媒体を作製した。 <Preparation of volume hologram recording medium>
A metal foil having a thickness of 10 μm is placed as a spacer on the upper, lower, left, and right ends of the slide glass, and the above-described composition for a volume hologram recording material is dropped at the center of the slide glass (an area sandwiched by the spacers) to form a volume hologram recording layer. did. Thereafter, another slide glass was placed so as to sandwich the formed volume hologram recording layer, thereby producing a volume hologram recording medium.
＜体積ホログラム記録時の各物性値の測定＞
　得られた体積ホログラム記録媒体に対し、図２に示す装置によって二光束干渉露光を行い、体積ホログラムの記録を試みた。体積ホログラム記録媒体に対し、波長５３２ｎｍのＮｄ：ＹＶＯ４レーザーを用いて、露光パワー密度２５０ｍＷ／ｃｍ２で二光束干渉露光（格子間隔１μｍ）を行った。Ｎｄ：ＹＶＯ４レーザーから出射した光はビームエキスパンダを経てハーフミラーで２本に分割され、それぞれミラーを経て体積ホログラム記録媒体に照射され、両光の干渉縞が記録され体積ホログラムを形成させた。
　同時に、体積ホログラム記録媒体が感光しない波長６３２．８ｎｍのヘリウムネオン（Ｈｅ－Ｎｅ）レーザーを体積ホログラム記録媒体に照射し、その回折光を光検出器で検出することによりホログラム形成過程をモニターし回折効率を評価した。また、露光後の回折効率の角度依存性を測定し、試料の露光後の膜厚を算出した。さらに、得られた回折効率と膜厚から、屈折率変調量（Δｎ）の露光時間変化と飽和屈折率変調量（Δｎｓａｔ）を評価した。結果を表１に併せて示す。また露光時間に対するΔｎの変化を図３に示す。 <Measurement of each physical property value at the time of volume hologram recording>
The obtained volume hologram recording medium was subjected to two-beam interference exposure using the apparatus shown in FIG. 2 to attempt to record a volume hologram. Two- beam interference exposure (lattice interval: 1 μm) was performed on the volume hologram recording medium at an exposure power density of 250 mW / cm 2 using an Nd: YVO 4 laser having a wavelength of 532 nm. The light emitted from the Nd: YVO 4 laser is split into two beams by a half mirror via a beam expander, and is irradiated on a volume hologram recording medium via each mirror, and interference fringes of both lights are recorded to form a volume hologram. .
At the same time, a helium-neon (He-Ne) laser having a wavelength of 632.8 nm to which the volume hologram recording medium is not exposed is irradiated on the volume hologram recording medium, and the diffracted light is detected by a photodetector to monitor the hologram formation process and diffract. The efficiency was evaluated. The angle dependence of the diffraction efficiency after exposure was measured, and the film thickness of the sample after exposure was calculated. Further, based on the obtained diffraction efficiency and film thickness, the change in exposure time of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn sat ) were evaluated. The results are shown in Table 1. FIG. 3 shows a change in Δn with respect to the exposure time.
［比較例１］
　４ＨＢＡ７６４ｍｇをＴＨＦＡ（密度１．０６４ｇ／ｃｍ３）７０４ｍｇ及びＮＶＰ（密度１．０４３ｇ／ｃｍ３）６０ｍｇに変更した以外は実施例１と同様の方法で、ＨＢ－ＴｍＤＡの体積分率が１９．９体積％となる体積ホログラム媒体を作製し、同様に評価した。結果を表１に併せて示す。また露光時間に対するΔｎの変化を図４に示す。 [Comparative Example 1]
4HBA764mg at THFA (density 1.064g / cm 3) 704mg and NVP (density 1.043 g / cm 3) was changed to 60mg in the same manner as in Example 1, the volume fraction of the HB-TMDA 19.9 A volume hologram medium having a volume% was prepared and evaluated in the same manner. The results are shown in Table 1. FIG. 4 shows a change in Δn with respect to the exposure time.
［比較例２］
　４ＨＢＡ７６４ｍｇをＭＭＡ７６４ｍｇに変更した以外は実施例１と同様の方法で、体積ホログラム記録材料用組成物の作製を試みた。しかし、ＨＢ－ＴｍＤＡが溶解せず均一な組成物が得られなかったため、以降の体積ホログラムの形成及び回折効率の評価は行えなかった。 [Comparative Example 2]
Production of a composition for a volume hologram recording material was attempted in the same manner as in Example 1 except that 764 mg of 4HBA was changed to 764 mg of MMA. However, since HB-TmDA did not dissolve and a uniform composition was not obtained, subsequent formation of a volume hologram and evaluation of diffraction efficiency could not be performed.
［比較例３］
　４ＨＢＡ７６４ｍｇをＢｎＭＡ７６４ｍｇに変更した以外は実施例１と同様の方法で、体積ホログラム記録材料用組成物の作製を試みた。しかし、ＨＢ－ＴｍＤＡが溶解せず均一な組成物が得られなかったため、以降の体積ホログラムの形成及び回折効率の評価は行えなかった。 [Comparative Example 3]
Production of a composition for a volume hologram recording material was attempted in the same manner as in Example 1 except that 764 mg of 4HBA was changed to 764 mg of BnMA. However, since HB-TmDA did not dissolve and a uniform composition was not obtained, subsequent formation of a volume hologram and evaluation of diffraction efficiency could not be performed.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表１に示すように、本発明の組成物（実施例１）は、エーテル構造を有するアクリルモノマー及びアミド構造を有するビニルモノマーを添加した組成物（比較例１）と比べて、極めて高い飽和屈折率変調量Δｎｓａｔを示すことが確認された。
　また、本発明のヒドロキシアルキル（メタ）アクリレートに替えて、無置換のアルキル（メタ）アクリレートを添加した組成物（比較例２）、アラルキル（メタ）アクリレートを添加した組成物（比較例３）においては、ハイパーブランチポリマーが溶解せず均一な組成物が得られないとする結果を得た。 As shown in Table 1, the composition of the present invention (Example 1) has an extremely high saturation refraction as compared with the composition in which an acrylic monomer having an ether structure and a vinyl monomer having an amide structure are added (Comparative Example 1). It was confirmed that the rate modulation amount Δn sat was exhibited.
In addition, in place of the hydroxyalkyl (meth) acrylate of the present invention, a composition containing an unsubstituted alkyl (meth) acrylate (Comparative Example 2) and a composition containing an aralkyl (meth) acrylate (Comparative Example 3) were used. Obtained a result that the hyperbranched polymer did not dissolve and a uniform composition was not obtained.
［実施例２］
　（ａ）（メタ）アクリル酸ヒドロキシアルキルとして、４ＨＢＡ３，９１８ｍｇ、（ｂ）重合性化合物として、ＥＤＰＨＡ１５９ｍｇ、（ｃ）トリアジン環含有ハイパーブランチポリマーとして、製造例１で得られたＨＢ－ＴｍＤＡ９１３ｍｇ、並びに（ｄ）光重合開始剤として、ＮＰＧ６．３６ｍｇ、また増感剤として、ＲＢ３．１８ｍｇを混合し、５０℃で２４時間撹拌することで、体積ホログラム記録材料用組成物を調製した。
　得られた組成物を用い、スペーサの厚さを５μｍに、露光パワー密度を５ｍＷ／ｃｍ２に、それぞれ変更した以外は実施例１と同様の方法で体積ホログラム記録媒体を作製し、屈折率変調量（Δｎ）の露光時間変化と飽和屈折率変調量（Δｎｓａｔ）を評価した。結果を表２に併せて示す。また露光時間に対するΔｎの変化を図５に示す。
　ここで、４ＨＢＡの密度は１．０４ｇ／ｃｍ３、ＥＤＰＨＡの密度は１．１５ｇ／ｃｍ３、ＨＢ－ＴｍＤＡの密度は１．３２ｇ／ｃｍ３であり、その体積はそれぞれ、４ＨＢＡ：３．９１８÷１．０４＝３．７６７ｃｍ３、ＥＤＰＨＡ：０．１５９÷１．１５＝０．１３８ｃｍ３、ＨＢ－ＴｍＤＡ：０．９１３÷１．３２＝０．６９２ｃｍ３であった。
　したがって、各重合性成分（４ＨＢＡ及びＥＤＰＨＡ）及びＨＢ－ＴｍＤＡの合計体積に占めるＨＢ－ＴｍＤＡの体積分率は、（０．６９２÷（３．７６７＋０．１３８＋０．６９２））×１００＝１５．０５、即ち１５．１体積％であった。 [Example 2]
(A) 4,918 mg of 4HBA as hydroxyalkyl (meth) acrylate, (b) 159 mg of EDPHA as a polymerizable compound, (c) 913 mg of HB-TmDA obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, and ( d) 6.36 mg of NPG as a photopolymerization initiator and 3.18 mg of RB as a sensitizer were mixed and stirred at 50 ° C. for 24 hours to prepare a composition for a volume hologram recording material.
Using the obtained composition, a volume hologram recording medium was prepared in the same manner as in Example 1 except that the thickness of the spacer was changed to 5 μm and the exposure power density was changed to 5 mW / cm 2 , and the refractive index modulation was performed. The exposure time change of the amount (Δn) and the saturated refractive index modulation amount (Δn sat ) were evaluated. The results are shown in Table 2. FIG. 5 shows a change in Δn with respect to the exposure time.
Here, the density of 4HBA is 1.04 g / cm 3 , the density of EDPHA is 1.15 g / cm 3 , the density of HB-TmDA is 1.32 g / cm 3 , and the volumes are 4HBA: 3.918, respectively. ÷ 1.04 = 3.767 cm 3 , EDPHA: 0.159 ÷ 1.15 = 0.138 cm 3 , HB-TmDA: 0.913 ÷ 1.32 = 0.692 cm 3 .
Therefore, the volume fraction of HB-TmDA in the total volume of each polymerizable component (4HBA and EDPHA) and HB-TmDA is (0.692 ÷ (3.767 + 0.138 + 0.692)) × 100 = 15.05. Ie, 15.1% by volume.
［実施例３～５］
　実施例２と同様の方法で、ＨＢ－ＴｍＤＡの体積分率が表２に記載の値となる体積ホログラム媒体を作製し、同様に評価した。結果を表２に併せて示す。また露光時間に対するΔｎの変化を図６（実施例３）、図７（実施例４）、図８（実施例５）に示す。 [Examples 3 to 5]
In the same manner as in Example 2, a volume hologram medium in which the volume fraction of HB-TmDA had the value shown in Table 2 was produced and evaluated in the same manner. The results are shown in Table 2. 6 (Example 3), FIG. 7 (Example 4), and FIG. 8 (Example 5) show changes in Δn with respect to the exposure time.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表２に示すように、本発明の組成物（実施例２～実施例５）は極めて高い飽和屈折率変調量Δｎｓａｔを示すことが確認され、（ｂ）重合性化合物としてエチレンオキシド変性ジペンタエリスリトールヘキサアクリレートと、（ｄ）光重合開始剤としてＮ－フェニルグリシン及び増感剤としてローズベンガルを採用することにより、実施例１の組成物（（ｂ）重合性化合物としてジペンタエリスリトールペンタアクリレート／ジペンタエリスリトールヘキサアクリレート混合物と、（ｃ）光重合開始剤としてビス（シクロペンタジエニル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウム）に比べて、より一層高い飽和屈折率変調量Δｎｓａｔを示すことが確認された。 As shown in Table 2, it was confirmed that the compositions of the present invention (Examples 2 to 5) exhibited an extremely high saturation refractive index modulation amount Δn sat , and (b) ethylene oxide-modified dipentaerythritol as a polymerizable compound By employing hexaacrylate, (d) N-phenylglycine as a photopolymerization initiator and rose bengal as a sensitizer, the composition of Example 1 ((b) dipentaerythritol pentaacrylate / diacrylate as a polymerizable compound) was used. Compared with pentaerythritol hexaacrylate mixture and (c) bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium as a photopolymerization initiator It was confirmed that a higher saturation refractive index modulation Δn sat was exhibited.
［実施例６］
　（ａ）（メタ）アクリル酸ヒドロキシアルキルとして、４ＨＢＡ３，６３２ｍｇ、（ｂ）重合性化合物として、ＥＤＰＨＡ１５７ｍｇ、（ｃ）トリアジン環含有ハイパーブランチポリマーとして、製造例１で得られたＨＢ－ＴｍＤＡ１，２０２ｍｇ、並びに（ｄ）光重合開始剤として、ＴＣＴ２３．５６ｍｇ、また増感剤として、ＤｉＳＣ３．１４ｍｇを混合し、５０℃で２４時間撹拌することで、体積ホログラム記録材料用組成物を調製した。
　ここで、４ＨＢＡの密度は１．０４ｇ／ｃｍ３、ＥＤＰＨＡの密度は１．１５ｇ／ｃｍ３、ＨＢ－ＴｍＤＡの密度は１．３２ｇ／ｃｍ３であり、その体積はそれぞれ、４ＨＢＡ：３．６３２÷１．０４＝３．４９２ｃｍ３、ＥＤＰＨＡ：０．１５７÷１．１５＝０．１３６ｃｍ３、ＨＢ－ＴｍＤＡ：１．２０２÷１．３２＝０．９１１ｃｍ３であった。
　したがって、各重合性成分（４ＨＢＡ及びＥＤＰＨＡ）及びＨＢ－ＴｍＤＡの合計体積に占めるＨＢ－ＴｍＤＡの体積分率は、（０．９１１÷（３．４９２＋０．１３６＋０．９１１））×１００＝２０．０７、即ち２０．１体積％であった。 [Example 6]
(A) 3,632 mg of 4HBA as hydroxyalkyl (meth) acrylate, (b) 157 mg of EDPHA as a polymerizable compound, (c) 1,202 mg of HB-TmDA obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, Further, (d) 23.56 mg of TCT as a photopolymerization initiator and 3.14 mg of DiSC as a sensitizer were mixed and stirred at 50 ° C. for 24 hours to prepare a composition for a volume hologram recording material.
Here, the density of 4HBA is 1.04 g / cm 3 , the density of EDPHA is 1.15 g / cm 3 , the density of HB-TmDA is 1.32 g / cm 3 , and the volumes are 4HBA: 3.632. ÷ 1.04 = 3.492 cm 3 , EDPHA: 0.157 ÷ 1.15 = 0.136 cm 3 , HB-TmDA: 1.202 ÷ 1.32 = 0.911 cm 3 .
Therefore, the volume fraction of HB-TmDA in the total volume of each polymerizable component (4HBA and EDPHA) and HB-TmDA is (0.911 ÷ (3.492 + 0.136 + 0.911)) × 100 = 20.07 That is, it was 20.1% by volume.
＜体積ホログラム記録媒体の作製＞
　得られた組成物を用い、スペーサの厚さを５μｍに変更した以外は実施例１と同様の方法で体積ホログラム記録媒体を作製した。 <Preparation of volume hologram recording medium>
Using the obtained composition, a volume hologram recording medium was produced in the same manner as in Example 1 except that the thickness of the spacer was changed to 5 μm.
＜体積ホログラム記録時の各物性値の測定＞
　得られた体積ホログラム記録媒体に対し、図９に示す装置によって二光束干渉露光を行い、体積ホログラムの記録を試みた。体積ホログラム記録媒体に対し、波長６４０ｎｍの固体レーザー［Ｃｏｂｏｌｔ社製　０５－０１　Ｂｏｌｅｒｏ］を用いて、露光パワー密度５ｍＷ／ｃｍ２で二光束干渉露光（格子間隔０．５μｍ）を行った。固体レーザーから出射した光はビームエキスパンダを経てハーフミラーで２本に分割され、それぞれミラーを経て体積ホログラム記録媒体に照射され、両光の干渉縞が記録され体積ホログラムを形成させた。
　同時に、体積ホログラム記録媒体が感光しない波長５３２ｎｍのＮｄ：ＹＶＯ４レーザーを体積ホログラム記録媒体に照射し、その回折光を光検出器で検出することによりホログラム形成過程をモニターし回折効率を評価した。また、露光後の回折効率の角度依存性を測定し、試料の露光後の膜厚を算出した。さらに、得られた回折効率と膜厚から、屈折率変調量（Δｎ）の露光時間変化と飽和屈折率変調量（Δｎｓａｔ）を評価した。結果を表３に併せて示す。また露光時間に対するΔｎの変化を図１０に示す。 <Measurement of each physical property value at the time of volume hologram recording>
The obtained volume hologram recording medium was subjected to two-beam interference exposure using the apparatus shown in FIG. 9 to attempt to record a volume hologram. Two- beam interference exposure (grating interval: 0.5 μm) was performed on the volume hologram recording medium with an exposure power density of 5 mW / cm 2 using a solid-state laser having a wavelength of 640 nm [05-01 Bolero, manufactured by Cobolt]. The light emitted from the solid-state laser was split into two light beams by a half mirror via a beam expander, and was applied to the volume hologram recording medium via the respective mirrors. The interference fringes of both lights were recorded to form a volume hologram.
At the same time, Nd wavelength 532nm of the volume hologram recording medium is not sensitive: a YVO 4 laser is irradiated to the volume hologram recording medium was evaluated monitored diffraction efficiency of the hologram formation process by detecting the diffracted light by the photodetector. The angle dependence of the diffraction efficiency after exposure was measured, and the film thickness of the sample after exposure was calculated. Further, based on the obtained diffraction efficiency and film thickness, the change in exposure time of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn sat ) were evaluated. The results are shown in Table 3. FIG. 10 shows a change in Δn with respect to the exposure time.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　本発明の体積ホログラム記録材料用組成物、及びそれらから得られる体積ホログラム記録媒体は、三次元画像表示、ウェアラブルディスプレイ、ビット情報の大容量メモリ、回折光学素子、その他に使用できる。 The composition for a volume hologram recording material of the present invention and the volume hologram recording medium obtained therefrom can be used for three-dimensional image display, wearable display, large-capacity bit information memory, diffractive optical element, and the like.
１　ホログラム記録媒体
２ａ　Ｎｄ：ＹＶＯ４レーザー
２ｂ　固体レーザー
３　ビームエキスパンダ
４ａ　Ｈｅ－Ｎｅレーザー
４ｂ　Ｎｄ：ＹＶＯ４レーザー
５，６，７，８，９，１０，１１　ミラー
１２　ビームサンプラー
１３　ハーフミラー
１４，１５　半波長板
１６，１７　偏光プリズム
１８，１９，２０　光検出器 Reference Signs List 1 hologram recording medium 2a Nd: YVO 4 laser 2b solid laser 3 beam expander 4a He-Ne laser 4b Nd: YVO 4 laser 5, 6, 7, 8, 9, 10, 11 mirror 12 beam sampler 13 half mirror 14, 15 Half- wave plate 16, 17 Polarizing prism 18, 19, 20 Photodetector

Claims (9)

  1. パターン露光によってパターンを形成するために使用される体積ホログラム記録材料用組成物であって、
    （ａ）（メタ）アクリル酸ヒドロキシアルキル、
    （ｂ）（ａ）成分とは異なる重合性化合物、
    （ｃ）トリアジン環含有ハイパーブランチポリマー及び
    （ｄ）光重合開始剤
    を含む体積ホログラム記録材料用組成物。     A volume hologram recording material composition used to form a pattern by pattern exposure,
    (A) hydroxyalkyl (meth) acrylate,
    (B) a polymerizable compound different from the component (a),
    A composition for a volume hologram recording material, comprising (c) a triazine ring-containing hyperbranched polymer and (d) a photopolymerization initiator.
  2. 前記（ａ）成分、前記（ｂ）成分、及び前記（ｃ）成分の合計体積に占める前記（ｃ）成分の割合が、３体積％以上、５０体積％以下である、請求項１に記載の体積ホログラム記録材料用組成物。 2. The method according to claim 1, wherein a ratio of the component (c) to a total volume of the component (a), the component (b), and the component (c) is 3% by volume or more and 50% by volume or less. Composition for volume hologram recording material.
  3. 前記パターン露光が干渉露光であり、該干渉露光によりホログラムを形成するために使用される、請求項１又は請求項２に記載の体積ホログラム記録材料用組成物。 The composition for a volume hologram recording material according to claim 1 or 2, wherein the pattern exposure is interference exposure, and the pattern exposure is used to form a hologram by the interference exposure.
  4. 前記（ｂ）（ａ）成分とは異なる重合性化合物が多官能（メタ）アクリレートである、請求項１乃至請求項３のうち何れか一項に記載の体積ホログラム記録材料用組成物。 The composition for a volume hologram recording material according to any one of claims 1 to 3, wherein the polymerizable compound different from the components (b) and (a) is a polyfunctional (meth) acrylate.
  5. 請求項１乃至請求項４のうち何れか１項に記載の体積ホログラム記録材料用組成物を含む体積ホログラム記録層。 A volume hologram recording layer comprising the composition for a volume hologram recording material according to any one of claims 1 to 4.
  6. 請求項５に記載の体積ホログラム記録層を含む体積ホログラム記録媒体。 A volume hologram recording medium comprising the volume hologram recording layer according to claim 5.
  7. 体積ホログラム記録層が、各々平面を有しそれら平面が対面する２枚の透明基体間に配置された構造である、請求項６に記載の体積ホログラム記録媒体。 7. The volume hologram recording medium according to claim 6, wherein the volume hologram recording layer has a structure in which each of the volume hologram recording layers has a plane and is disposed between two transparent substrates facing each other.
  8. 請求項１乃至請求項４のうち何れか一項に記載の体積ホログラム記録材料用組成物を、支持体に塗布し塗布膜を形成する工程、及び前記塗布膜にパターン露光する工程を含む、パターンの形成方法。 A pattern comprising a step of applying the composition for a volume hologram recording material according to any one of claims 1 to 4 to a support to form a coating film, and a step of patternwise exposing the coating film. Formation method.
  9. 前記パターン露光が干渉露光である、請求項８に記載のパターンの形成方法。 9. The pattern forming method according to claim 8, wherein the pattern exposure is interference exposure.
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US20100248088A1 (en) * 2009-03-25 2010-09-30 Sony Dadc Austria Ag Photopolymerisable system for hologram formation
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EP1489144A1 (en) * 2003-06-18 2004-12-22 DSM IP Assets B.V. Water-soluble polymeric dye
US20100248088A1 (en) * 2009-03-25 2010-09-30 Sony Dadc Austria Ag Photopolymerisable system for hologram formation
JP2013519111A (en) * 2010-02-02 2013-05-23 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Photopolymer composition containing triazine-based writing monomer
JP2014197191A (en) * 2013-03-08 2014-10-16 国立大学法人電気通信大学 Composition for volume hologram recording material which contains triazine ring-containing hyperbranched polymer
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