JP6471390B2 - Composition for volume hologram recording material containing hyperbranched polymer containing triazine ring - Google Patents

Description

  The present invention provides a composition for a volume hologram recording material capable of forming a pattern in which movement of each component in the composition is caused by pattern exposure and the 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 composition for hologram recording material and a volume hologram recording medium comprising the recording layer.

  A holographic diffraction grating (hologram) is a light-dark (interference) pattern recorded on a photosensitive material or the like as a pattern of refractive index or absorptivity. Since it has multiple functions, it is a diffractive optical element, holographic optical memory, Many 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, and head-up displays. In these application fields, a large change in refractive index and high recording sensitivity are usually required.

As conventional typical hologram recording material compositions, dichromated gelatin photosensitive materials and bleached silver salt photosensitive materials have been used. These have high diffraction efficiency, but have a drawback in that the processing at the time of hologram production is complicated, and in particular, wet development processing is necessary.
As a dry hologram photosensitive material that overcomes these disadvantages, the DuPont Omnidex series is widely known. This material has a radical polymerization monomer, a binder polymer, a photo radical polymerization initiator, and a sensitizing dye as main components, and records a hologram using a difference in refractive index between the radical polymerization monomer and the binder polymer. That is, when the photosensitive composition formed into a film is subjected to interference exposure, radical polymerization is started in a portion where light is strong, and accordingly, a concentration gradient of the radical polymerization monomer is generated, and radicals are generated from a portion where light is weak to a portion where light is strong. The diffusion transfer of the polymerization monomer occurs. As a result, depending on the intensity of the interference light, the density of the radical polymerization monomer and the density of the polymerized polymer can be made dense, and a hologram is formed as the difference in refractive index between them and the binder polymer. Although this material system has high performance as a currently reported hologram photopolymer, it is pointed out that it is limited to a thickness of about 30 μm and has problems in heat resistance and transparency.

  In addition, a material system using radical polymerization and cationic polymerization in combination (see Patent Document 1) and a material system using cationic polymerization (see Patent Document 2) have been reported. Since they are not compatible with each other, the hologram recording film formed of this material system has problems such as a decrease in transparency due to phase separation and an increase in scattering loss based thereon. Furthermore, mechanical strength and environmental stability are still insufficient.

  Moreover, the material system which used the inorganic substance network and the photopolymerizable monomer together is disclosed (refer patent document 3). When an inorganic material that can form a network is used as a binder, this material has the advantages of being excellent in heat resistance, environmental resistance and mechanical strength, and having a large difference in refractive index from a photopolymerizable organic monomer. The hologram recording film formed by the system is rather fragile and has problems of poor flexibility, workability, 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). However, in the present invention, it is necessary to give the matrix fluidity, not only the solidity is bad, but also the interface adhesion between the metal particle interface and the solid matrix is bad, brittle, and water penetrates into the interface. is there.

  Further, a hologram recording material using an organic-inorganic hybrid polymer and organometallic fine particles having a photopolymerization reactive group is disclosed (see Patent Document 5). However, in the present invention, heating and ultraviolet polymerization are required to fix the interference fringes, and there is a problem as an industrial process.

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 Document 6, Patent Document 7, and Non-Patent Document 1).
Further, a low-shrinkage 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).
However, even with these materials, there is a problem that sufficient diffraction efficiency is not obtained.

Japanese Patent Laid-Open No. 5-107999 US Pat. No. 5,759,721 JP-A-6-019040 JP 2000-508883 gazette JP 2002-236440 A JP 2003-084551 A Japanese Patent Laying-Open No. 2005-099612 JP 2010-250246 A

Applied Physics Letters (Appl. Phys. Lett.), 2002, Vol. 81, p. 4121-4123

  In the volume hologram recording material, a triazine ring-containing hyperbranched polymer having a low agglomeration property and a very high refractive index is used as fine particles, so that a hologram with a very low light scattering loss and a high diffraction efficiency is permanently obtained. An object of the present invention is to provide a composition for a volume hologram recording material that can be formed, and a hologram recording medium using the composition.

As a result of intensive studies to achieve the above object, the present inventors 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, wherein (a) a polymerizable compound, (b) a photopolymerization initiator, (c) a triazine ring The present invention relates to a composition for a volume hologram recording material comprising a containing hyperbranched polymer and (d) a vinyl monomer having an ether or amide structure and / or a (meth) acrylic monomer.
As a second aspect, the refractive index of the polymer of (a) a polymerizable compound and (d) a vinyl monomer and / or (meth) acryl monomer having an ether or amide structure, and (c) a triazine ring-containing hyperbranched polymer. The volume hologram recording material composition according to the first aspect, which has a difference from the refractive index of 0.01 to 0.6.
As a third aspect, (a) a polymer of a polymerizable compound, (c) a triazine ring-containing hyperbranched polymer, and (d) a polymer of a vinyl monomer and / or (meth) acrylic monomer having an ether or amide structure. The volume hologram recording material composition according to the first aspect or the second aspect, wherein the ratio of the (c) triazine ring-containing hyperbranched polymer in the total volume is 3% by volume or more and 50% by volume or less.
As a fourth aspect, the composition for volume hologram recording material according to any one of the first aspect to the third aspect, wherein the pattern exposure is interference exposure, and is used for forming a hologram by the interference exposure. Related to things.
As a 5th viewpoint, it is related with the volume hologram recording layer containing the composition for volume hologram recording materials of any one of the 1st viewpoint thru | or a 4th viewpoint.
As a sixth aspect, the present invention relates to a volume hologram recording medium including the volume hologram recording layer described in 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 arranged between two transparent substrates each having a flat surface and facing each other.
As an eighth aspect, a step of applying the composition for volume hologram recording material according to any one of the first aspect to the fourth aspect to a support to form a coating film, and pattern exposure to the coating film The present invention relates to a pattern forming method including a process.
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.

  According to the present invention, as a fine particle, a triazine ring-containing hyperbranched polymer having a very low refractive index and a very high refractive index is combined with a vinyl monomer having an ether or amide structure and / or a (meth) acryl monomer, and a polymerizable compound or the like. By dispersing in a component, it is possible to provide a composition for volume hologram recording material and a volume hologram recording medium that can permanently form a hologram with low light scattering loss and high diffraction efficiency.

1 is a diagram showing a ¹ H NMR spectrum of HB-TmDA40 obtained in Synthesis Example 1. FIG. FIG. 2 is a diagram showing the results of TG-DTA measurement of HB-TmDA40 obtained in Synthesis Example 1. FIG. 3 shows the volume hologram recording apparatus used in the example. FIG. 4 is a graph showing changes in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained using the volume hologram recording medium of Example 1 (volume fraction of HB-TmDA40: 20.1 vol%). It is. FIG. 5 is a graph showing changes in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained using the volume hologram recording medium of Example 2 (volume fraction of HB-TmDA40: 12.2% by volume). It is. FIG. 6 is a graph showing a change in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained using the volume hologram recording medium of Example 3 (volume fraction of HB-TmDA40: 15.6 vol%). It is. FIG. 7 is a graph showing changes in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained using the volume hologram recording medium of Example 4 (volume fraction of HB-TmDA40: 17.9% by volume). It is. FIG. 8 is a graph showing the change in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained using the volume hologram recording medium of Example 5 (volume fraction of HB-TmDA40: 22.9% by volume). It is. FIG. 9 is a diagram showing the change in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained using the volume hologram recording medium of the comparative example (not including HB-TmDA40). FIG. 10 is a diagram showing the value of the saturated refractive index modulation amount Δn _sat with respect to the volume fraction (volume%) of the fine particles (HB-TmDA40).

  The composition for volume hologram recording material of the present invention comprises (a) a polymerizable compound, (b) a photopolymerization initiator, (c) a triazine ring-containing hyperbranched polymer, and (d) a vinyl monomer having an ether or amide structure and / or Or it is comprised including a (meth) acryl monomer.

The details of the recording principle of the volume hologram in the volume hologram recording medium using the composition for volume hologram recording material are not clear, but are presumed as follows.
A pattern such as a hologram is formed by recording a light interference pattern using a difference in refractive index between at least two components contained in the recording layer. Therefore, a polymer produced from a polymerizable component such as the above-described polymerizable compound under the conditions of pattern exposure for forming a pattern (for example, under the condition of interference exposure for hologram recording), for example, in the case of the present invention It is important that there is a large difference between the refractive index of the triazine ring-containing hyperbranched polymer.

That is, in the present invention, the refractive index of a triazine ring-containing hyperbranched polymer and the refractive index of a polymer generated from a polymerizable component such as a polymerizable compound with respect to the wavelength of light used for interference exposure for hologram recording, Is required to be 0.01 to 0.6. Preferably, the difference in refractive index is more preferably 0.02 to 0.5 or 0.03 to 0.4. From such a viewpoint, a suitable triazine ring-containing hyperbranched polymer and polymerizable component used in the present invention are selected.
The triazine ring-containing hyperbranched polymer has a relatively high refractive index. 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 used in the present invention is relatively smaller than the above numerical value. For example, the refractive index for light having a wavelength of 589 nm is 1.3 or more. A polymerizable component that gives a polymer that is 7 or less 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.

  The refractive index of the polymer is determined by applying light used for interference exposure for hologram recording after coating a composition comprising a polymerizable component and a photopolymerization initiator on a support, drying as necessary. It can be determined by obtaining a polymer by subjecting the composition to spatially uniform exposure under the conditions used, and 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 suitable for the composition for hologram recording material of the present invention (polymerizable compound, etc.) ), And a triazine ring-containing hyperbranched polymer, respectively.

  Hereinafter, each component contained in the composition for volume hologram recording material of the present invention will be described.

[(A) Polymerizable compound]
The polymerizable compound in the present invention is not particularly limited as long as it is a compound having one or more, preferably 1 to 6, polymerizable sites that are polymerized by the action of a photopolymerization initiator. Examples of the polymerizable moiety include an ethylenically unsaturated bond which is a radical polymerizable moiety.
The polymerizable compound in the present invention means a compound that is not a so-called non-reactive polymer substance, and therefore, 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 radical polymerizable site or a cationic polymerizable site.
Examples of the polymerizable compound having a radically polymerizable moiety include compounds having an ethylenically unsaturated bond. Examples of the polymerizable compound having a cationically polymerizable moiety include compounds having a vinyl thioether structure or a cyclic ether structure such as an epoxy ring or an oxetane ring.

<Polymerizable compound having radically polymerizable site>
Examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acid; unsaturated carboxylic ester compound; ester compound of aliphatic polyhydroxy compound and unsaturated carboxylic acid; aromatic polyhydroxy compound and unsaturated carboxylic acid And ester compounds obtained by esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polyvalent carboxylic acids.

  Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.

  Specific examples of the unsaturated carboxylic acid ester compound include phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2 -Acrylic acid ester compounds such as acryloyloxyethylphthalic acid and isobornyl acrylate. In addition, a methacrylic acid ester compound in which the acrylate part of these exemplary compounds is replaced with methacrylate, an itaconic acid ester compound similarly replaced with itaconate, a crotonic acid ester compound replaced with crotonate, a maleic acid ester compound replaced with maleate, etc. Can be mentioned.

  Specific examples of the ester compound of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol. Examples thereof include acrylic ester compounds such as triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, methacrylic acid ester compounds in which the acrylate portion of these exemplified compounds is replaced with methacrylate, itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, maleic acid ester compounds in place of maleate, etc. It is done.

  Examples of the ester compound of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

  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 is not necessarily a single substance, but is representative. 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 condensates of butanediol and glycerin.

In addition to the above ester compounds, as compounds having an ethylenically unsaturated bond, urethane compounds that can be obtained by reaction of polyvalent isocyanates and hydroxyalkyl unsaturated carboxylic acid esters, polyhydric epoxy compounds and hydroxyalkyl unsaturated carboxylic acids. Mention may be made of compounds obtainable by reaction with acid esters. Examples of the urethane compound include, for example, EBECRYL (trade name) series urethane acrylate manufactured by Daicel-Cytec Co., Ltd., and specifically, by using, for example, EBECRYL 8301, the dispersibility is excellent. Diffraction efficiency can be obtained.
Other examples of the compound having an ethylenically unsaturated bond used in the present invention include allyl ester compounds such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

In the present invention, an acrylic ester compound and a methacrylic ester compound are particularly preferable as the compound having an ethylenically unsaturated bond.
These compounds having an ethylenically unsaturated bond may be used alone or in combination as necessary.

<Polymerizable compound having a cationically polymerizable moiety>
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, 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 perfluorohexane di 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-ethylenedi Oxy-bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4 Epoxycyclohexanecarboxylate), bis (3,4 -Epoxycyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether and the like.

  Examples of the compound having an oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3,3-diethyloxetane, 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 moiety may be used alone or in combination as necessary.

<Polymerizable compound>
In the present invention, the polymerizable compound as the component (a) may be used alone or in combination of two or more.
Further, as component (a), a compound having one polymerizable moiety and a compound having two or more polymerizable moieties (bifunctional or more polymerizable compound) are used in combination (c) described later. Diffusion of the triazine ring-containing hyperbranched polymer occurs rapidly, and characteristics such as diffraction efficiency become a more preferable form. However, the use amount (mass) of the bifunctional or higher polymerizable compound is preferably up to 10 times the mass (mass) of the total mass of the composition excluding the bifunctional or higher polymerizable compound. When the amount used is increased, the amount of dispersion of the (c) triazine ring-containing hyperbranched polymer is relatively reduced, and good characteristics such as diffraction efficiency cannot be obtained.
Examples of the bifunctional or higher polymerizable compound include compounds having two or more polymerizable sites in the above-described polymerizable compound having a radical polymerizable site or a compound having a cationic polymerizable compound.

[(B) Photopolymerization initiator]
The photopolymerization initiator in the present invention is not particularly limited as long as it is a compound having a function capable of initiating polymerization of the polymerizable compound (a) by pattern exposure described in detail later.
When using a compound having an ethylenically unsaturated bond, which is a radically polymerizable site, as the polymerizable compound, a photoradical initiator that generates an active radical during pattern exposure is basically used as the photopolymerization initiator. It is done.
In addition, 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, the photopolymerization initiator is basically a Lewis acid or Bronsted acid during pattern exposure. A photoacid generator that generates

<Radical radical polymerization initiator>
The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates an active radical at the time of pattern exposure. For example, a benzoin compound, an α-aminoalkylphenone compound, a thioxanthone compound, an azo compound, an azide compound , Diazo compounds, o-quinonediazide compounds, acylphosphine oxide compounds, oxime ester compounds, organic peroxides, benzophenones, biscoumarins, bisimidazole compounds, titanocene compounds, thiol compounds, halogenated hydrocarbon compounds, trichloro Methyltriazine compounds or onium salt compounds such as iodonium salt compounds and sulfonium salt compounds are used. Of these, titanocene compounds are preferred. A radical photopolymerization initiator may be used alone or in combination of two or more as required.

  The titanocene compound is not particularly limited. Specifically, 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-trifluoro Phenyl) 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 (methylsilane) Lopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (2,6-difluorophenyl) bis (methylcyclopentadienyl) titanium, bis (cyclopentadienyl) bis (2,6- And difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.

Examples of benzoin compounds include benzoin ethyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON etc. can be mentioned.

  Examples of the α-aminoalkylphenone compounds include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino And phenyl) butan-1-one.

  Examples of the thioxanthone compound include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl. Examples include thioxanthone.

  Examples of the azo compound include 2,2′-azobis (2-aminodipropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxyethyl). ) -2-methylpropionamidine], dimethyl 2,2′-azobisisobutyrate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 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-imidazolin-2-yl) Propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] sulfate 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.

  Examples of the azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidodiphenyl sulfide, 2 , 6-bis (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidostilbene, and the like.

  Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4- (dimethylamino) benzene chloride, 1-diazo-4- (diethylamino). Examples thereof include benzeneborofluoride.

  Examples of the o-quinonediazide compounds include 1,2-naphthoquinonediazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester, 1,2-naphthoquinonediazide (2 ) -4-sulfonyl chloride and the like.

  Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, and the like.

  Examples of oxime ester compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl. And -6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

  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, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.

  Biscumarins include, for example, 3,3′-carbonylbis (7- (diethylamino) -2H-chromen-2-one) and the like, which is a product of BC (CAS [63226-13-1] manufactured by Midori Chemical Co., Ltd. ).

  Examples of the bisimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) -1,2′-biimidazole, Examples include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

<Photo acid generator>
The photoacid generator is not particularly limited as long as it is a compound that generates a Lewis acid or a Bronsted acid during pattern exposure. For example, an onium salt compound such as a diaryliodonium salt compound, a triarylsulfonium salt compound, a diazonium salt compound, Examples thereof include iron arene complex compounds.

  Examples of the diaryliodonium salt compound include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyliodonium, (4-methylphenyl) [ Examples thereof include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like of iodonium such as 4- (2-methylpropyl) phenyl] iodonium and 3,3′-dinitrophenyliodonium.

  Examples of the triarylsulfonium salt compound include triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium, and the like. Examples of sulfonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.

Examples of the iron arene complex compound include biscyclopentadienyl- (η ⁶ -isopropylbenzene) -iron (II) hexafluorophosphate.

<Photopolymerization initiator>
These photopolymerization initiators such as photoradical polymerization initiators and photoacid generators may be used alone or in admixture of two or more if necessary.
The blending amount of the photopolymerization initiator in the composition for volume hologram recording material of the present invention is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to (a) the polymerizable compound.

[(C) Triazine ring-containing hyperbranched polymer]
The composition for volume hologram recording material of the present invention contains (c) a triazine ring-containing hyperbranched polymer as an essential component.
The component (c) has a refractive index of a polymerizable component, that is, a polymer of the (a) polymerizable compound and a vinyl monomer and / or (meth) acrylic monomer having an ether or amide structure described later (d). It is preferable to have a refractive index that makes a difference of 0.01 or more and 0.6 or less with respect to the refractive index.
The amount of component (c) contained in the composition for volume hologram recording material is as follows: (a) polymer of polymerizable compound, (c) triazine ring-containing hyperbranched polymer and (d) ether or The proportion of the vinyl monomer and / or (meth) acrylic monomer polymer having an amide structure in the total volume 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. It is.

As a triazine ring containing hyperbranched polymer, the polymer containing the repeating unit structure represented by following formula (1) is preferable.
In the above formula (1), R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.

In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but the number of carbon atoms is preferably 1 to 20, and considering the fact that the heat resistance of the polymer is further increased, the number of carbon atoms is 1 10 is more preferable, and 1 to 3 is even more preferable. The structure may be any of linear, branched, and cyclic.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, and 1-methyl. -Cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -N-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl -Cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl -Cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1- Dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl -N-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3 -Methyl-cyclopentyl group, 1- Til-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3- Dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2 -Methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclo A propyl group, 2-ethyl-3-methyl-cyclopropyl group, etc. are mentioned.

Although the number of carbon atoms of the alkoxy group is not particularly limited, the number of carbon atoms is preferably 1 to 20, and in view of further improving the heat resistance of the polymer, the number of carbon atoms is 1 to 10. More preferably, it is more preferably 1 to 3. Further, the structure of the alkyl moiety may be any of linear, branched or cyclic.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl -N-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2- Dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy Group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2- Methyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1 , 2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, etc. Can be mentioned.

Although the number of carbon atoms of the aryl group is not particularly limited, it is preferably 6 to 40 carbon atoms, and in view of further improving the heat resistance of the polymer, the number of carbon atoms is 6 to 16. More preferably, it is 6-13.
Specific examples of the aryl group include a phenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, and a p-methoxy group. Phenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, Examples include 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

The number of carbon atoms in the aralkyl group is not particularly limited, but the number of carbon atoms is preferably 7 to 20, and the alkyl portion may be linear, branched or cyclic.
Specific examples thereof include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenylmethyl group. 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.

In the above formula (1), Ar represents at least one divalent group selected from the group represented by the following formulas (2) to (13).

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 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 number of 1 Represents an alkyl group which may have a branched structure of 1 to 10 (provided that R ⁹⁵ and R ⁹⁶ may form a ring together with the carbon atoms to be bonded)), 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 of 1 to 10 carbon atoms.
Examples of these alkyl groups and alkoxy groups 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.

In the above formula, X ¹ and X ² are each independently a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or formula (14)
(Wherein R ^{99 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 that may have a branched structure of 1 to 10, Y ¹ and Y ² may independently have a single bond or a branched structure of 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 that 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, and a pentamethylene group.

  Suitable Ar in the formula (1) in the present invention includes at least one selected from groups represented by formulas (2), (5) to (13), and the formulas (2) and (5) , (7), (8), and at least one selected from the groups represented by (11) to (13) is more preferable.

  Specific examples of the aryl group (Ar) represented by the above formulas (2) to (13) include those represented by the following formula, but are not limited thereto.

  Among these, an aryl group represented by the following formula is more preferable because a hyperbranched polymer exhibiting a higher refractive index can be obtained.

Among them, as a suitable repeating unit structure contained in the (c) triazine ring-containing hyperbranched polymer, in the repeating unit structure represented by the formula (1), Ar is a divalent group represented by the formula (2). Some, 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 particularly preferred repeating unit structure includes a repeating unit structure represented by the following formula (16), and among them, a triazine ring-containing hyperbranched polymer containing a repeating unit structure represented by the following formula (17) is optimal. is there.

(In the formula, R and R ′ represent the same meaning as described above.)

Although the weight average molecular weight of the (c) triazine ring containing hyperbranched polymer in this invention is not specifically limited, 500-500,000 are preferable, Furthermore, 500-100,000 are preferable, While improving heat resistance more. From the viewpoint of reducing the shrinkage rate, 2,000 or more is preferable, and from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution, 50,000 or less is preferable, and 30,000 or less is more preferable. Furthermore, 10,000 or less is preferable.
In addition, the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.

  The (c) triazine ring-containing hyperbranched polymer can be produced by the technique disclosed in International Publication No. 2010/128661. For example, as shown in Scheme 1 below, by reacting cyanuric halide (18) and m-phenylenediamine compound (19) in a suitable organic solvent, a repeating unit structure (17 A triazine ring-containing hyperbranched polymer having ') can be obtained.

(In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)

[(D) Vinyl monomer or (meth) acrylic monomer having ether or amide structure]
The composition for volume hologram recording material of the present invention can disperse the (c) triazine ring-containing hyperbranched polymer, and can be dispersed together with the component (c) in the polymerizable compound (a) ( d) as an essential component.
From the viewpoint of having such properties, examples of the component (d) include vinyl monomers or (meth) acrylic monomers having an ether or amide structure.
In the present specification, the (meth) acrylic monomer means both an acrylic monomer and a methacrylic monomer.

The component (compound) (d) is not particularly limited as long as it is a vinyl monomer having an ether structure or an amide structure, or a (meth) acryl monomer having an ether structure or an amide structure. For example, 2-chloroethyl = vinyl = Compounds containing vinyl ether structures such as ether, n-butyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, trimethylolethane trivinyl ether, vinyl glycidyl ether; N-vinylformamide (NVF), N-vinyl N-vinylamides such as acetamide (NVA) and N-vinylpyrrolidone (NVP); N-allylamides such as N-allylformamide and N-allylacetamide; polyethylene glycol mono (meth) acrylate Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-co-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-co-propylene glycol) Di (meth) acrylate, poly (ethylene glycol-co-tetramethylene glycol) mono (meth) acrylate, poly (ethylene glycol-co-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-co-tetramethylene glycol) ) Glycol (meth) acrylates such as mono (meth) acrylate, poly (propylene glycol-co-tetramethylene glycol) di (meth) acrylate Cyclic ether group-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, amide compounds of aliphatic polyamine compounds and (meth) acrylic acid, (meth) acrylamide, N-methyl (meth) acrylamide N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, ethylenebis ( Examples include acrylamides such as (meth) acrylamide.
Among these, N-vinylamides and cyclic ether group-containing (meth) acrylates are particularly preferable, and N-vinylpyrrolidone (NVP) and tetrahydrofurfuryl (meth) acrylate are more preferable.
These vinyl monomers or (meth) acrylic monomers having an ether or amide structure may be used alone or in combination as necessary.

  The blending amount of the vinyl monomer or (meth) acrylic monomer having (d) ether or amide structure in the composition for volume hologram recording material of the present invention is 0.01 to 1, with respect to 1 part by weight of the polymerizable compound (a). 000 parts by mass, preferably 0.1 to 1,000 parts by mass, more preferably 1 to 1,000 parts by mass.

[Volume hologram recording medium]
The present invention is also directed to a volume hologram recording layer containing a composition for volume hologram recording material containing the components (a) to (d) and a volume hologram recording medium containing the recording layer.
In addition to the components (a) to (d), additives such as a sensitizer, a chain transfer agent, a plasticizer, and a colorant are added to the recording layer in the volume hologram recording medium of the present invention as necessary. Also good. In addition, a binder resin may be added as a binder in order to make the film thickness uniform and allow the interference film formed by polymerization by light irradiation to exist stably.

  The binder resin preferably has good compatibility with the resin components (components (a) and (d)). Specific examples thereof include chlorinated polyethylene, polymethyl (meth) acrylate, methyl (meth) acrylate and other (meta). ) 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.

In order to make a volume hologram recording layer and a volume hologram recording medium using the volume hologram recording composition of the present invention, the components (a) to (d) are mixed with a sensitizer and a binder resin, if necessary. Then, it is coated on the transparent substrate (support) without solvent as it is, or a solvent or additive is added to these mixtures to form a so-called varnish, which is coated on the transparent substrate, dried and then coated 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 a volume hologram recording layer may be arranged between the 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 with respect to the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve solvent; 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, ethyl-2- Ester solvents such as roxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate; alcohol solvents such as butanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol; methyl isobutyl ketone, cyclohexanone , Ketone solvents such as methyl amyl ketone; highly polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; or mixed solvents thereof; The thing etc. which added the hydrocarbon are mentioned.
The ratio of the amount of the solvent used is usually in the range of about 1 to 20 times in terms of mass ratio with respect to the total amount of the volume hologram material composition of the present embodiment.

  As the transparent substrate, a transparent glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene film, or the like is used. As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used.

  As the protective layer, a known technique for preventing adverse effects such as a decrease in sensitivity due to oxygen and deterioration in storage stability, for example, application 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 volume hologram recording material.
That is, the method includes a step of coating the volume hologram recording material composition on a support to form a coating film, and a pattern exposure step on the coating film, and the pattern exposure is particularly interference exposure. Is preferred.
As the support, those mentioned as the above-mentioned transparent substrate can be preferably used, and as the method for coating on the support, the above-mentioned coating method on the transparent substrate can be mentioned.

As described above, as a composition for volume hologram recording, a composition composed of a plurality of functional monomers having different refractive indexes and a composition composed of a liquid organic substance and a functional monomer are known. In order to obtain a hologram with high diffraction efficiency using such a composition, it is necessary to increase the difference in refractive index between the area corresponding to the bright part and the area corresponding to the dark part of the interference fringes. However, since the refractive index of organic substances proposed heretofore is usually limited to about 1.3 to 1.6, it is said that there is a limit in increasing the difference in refractive index in hologram recording materials composed of combinations of organic substances. It was.
The triazine ring-containing hyperbranched polymer used in the present invention has a high refractive index exceeding 1.7. Therefore, even when combined with organic substances (resin components, etc.) that are considered to be limited in the past, the refractive index difference is greatly increased. Therefore, a hologram having a high diffracted light rate can be obtained.

EXAMPLES Hereinafter, although a synthesis example and an Example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[ ¹ H NMR]
Apparatus: Varian NMR System 400NB (400 MHz) (currently manufactured by Agilent Technologies)
JEOL-ECA700 (700MHz)
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran (hereinafter THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [Ellipsometer]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE [differential thermobalance (TG-DTA)] manufactured by JA Woollam Japan
Device: TG-8120, manufactured by Rigaku Corporation
Temperature increase rate: 10 ° C / min Measurement temperature: 25 ° C-750 ° C
[Film density measurement XRR]
Device: D8 DISCOVER (Bruker AXS Co., Ltd.)
Tube voltage-current: 50 kV-100 mA
Measurement range: 0.2-3,000 deg (2θ)
Step width: 0.005 deg (2θ)
time / step: 0.5 seconds / step

[1] Synthesis of triazine ring-containing hyperbranched polymer [Synthesis Example 1] Synthesis of HB-TmDA40

Under nitrogen, 456.02 g of dimethylacetamide (DMAc) was added to a 1000 mL four-necked flask, cooled to −10 ° C. with an acetone-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1]. (84.83 g, 0.460 mol, manufactured by Eponic Degussa) was added and dissolved. Thereafter, m-phenylenediamine [2] (62.18 g, 0.575 mol) and aniline (14.57 g, 0.156 mol) separately dissolved in 304.01 g of DMAc were added dropwise to the four-necked flask and stirred for 30 minutes after the addition. Thus, a reaction solution was obtained.
This reaction solution was added dropwise to a 2000 mL four-necked flask that had been previously added with 621.85 g of DMAc and heated to 85 ° C. in an oil bath with a liquid feed pump over 1 hour, and then stirred for 1 hour for polymerization. Thereafter, aniline (113.95 g, 1.224 mol) was added, and then stirred for 1 hour to complete the reaction.
After cooling to room temperature with an ice bath, triethylamine (116.36 g, 1.15 mol) was added dropwise, and after 30 minutes of stirring, hydrochloric acid was quenched. Thereafter, the precipitated hydrochloride was removed by filtration. The filtered reaction solution was reprecipitated into a mixed solution of 28% aqueous ammonia (279.29 g) and ion-exchanged water 8820 g. The precipitate was filtered, dried at 150 ° C. for 8 hours in a vacuum dryer, redissolved in 833.1 g of THF, and reprecipitated in 6665 g of ion-exchanged water. The resulting precipitate was filtered and dried at 150 ° C. for 25 hours with a vacuum drier to obtain 118.0 g of the target polymer compound fine particles [3] (hereinafter abbreviated as HB-TmDA40).
The measurement result of the ¹ H-NMR spectrum of HB-TmDA40 is shown in FIG. The obtained HB-TmDA40 is a compound having a repeating unit structure represented by the above formula (1). The weight average molecular weight Mw measured in terms of polystyrene by GPC of HB-TmDA40 was 4,300, and the polydispersity Mw / Mn was 3.44. Moreover, the density of HB-TmDA40 obtained from the film density measurement was 1.32 g / cm ³ .

(1) Heat resistance test When TG-DTA measurement was performed on HB-TmDA40 obtained in Synthesis Example 1, the 5% weight loss temperature (Td _5% ) was 419 ° C. The obtained results are shown in FIG. 2 (2) Refractive index measurement 0.5 g of HB-TmDA40 obtained in Synthesis Example 1 was dissolved in 4.5 g of cyclohexanone to obtain a light yellow transparent solution (polymer varnish). The obtained polymer varnish was spin-coated on a glass substrate at 200 rpm for 5 seconds and 2000 rpm for 30 seconds using a spin coater, and the solvent was removed by heating at 150 ° C. for 1 minute and 250 ° C. for 5 minutes to obtain a coating film. It was. When the refractive index of the obtained film was measured, the refractive index at 550 nm was 1.790.

[Production Example 1]
Under nitrogen, in a 200 mL flask, 30 parts by mass of HB-TmDA40, 66 parts by mass of tetrahydrofurfuryl acrylate (hereinafter, THF-A) [manufactured by Kyoeisha Chemical Co., Ltd.], 4 parts by mass of N-vinylpyrrolidone (hereinafter, NVP) [ Pure Chemical Co., Ltd.] was added, heated to 60 ° C. in an oil bath, and stirred for 24 hours to obtain an acrylic monomer dispersion of HB-TmDA40.

<Example 1>
[Preparation of composition for volume hologram recording material]
To 1.067 g of HB-TmDA40 acrylic monomer dispersion (hyperbranched polymer concentration: 30.0% by mass) prepared in Production Example 1, 17 mg of NVP was added as (d), and (a) as a polymerizable compound, dipenta Erythritol hexaacrylate (DPHA) 303 mg, (b) As a photopolymerization initiator, bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (Ciba Japan) Co., Ltd., trade name: Irgacure 784) 3.1 mg was added and dissolved to prepare a volume hologram recording material composition.

At a wavelength of 589 nm, the refractive index of HB-TmDA40 is 1.79, the refractive index of the polymer of the polymerizable components (DPHA, THF-A and NVP) is 1.53, and the refractive index difference between them is 0.26. Met.
The density of the polymer of the polymerizable compound (DPHA) is 1.186g / cm ^3, since the density of the HB-TmDA40 is 1.32 g / cm ³ as described above, each of the volume, the polymerizable compound ^{: 0.303 / 1.186 = 0.255cm 3,} HB-TmDA40: 1.067 was × 0.3 / 1.32 = 0.243cm ^3. The total volume of THF-A (1.067 × 0.66 = 0.704 g) and NVP (1.067 × 0.04 + 0.017 = 0.060 g) used was 0.708 cm ³ .
Therefore, the volume fraction of HB-TmDA40 in the total volume of the polymerizable components (DPHA, THF-A and NVP) and HB-TmDA40 is [0.243 / (0.255 + 0.243 + 0.708)] × 100 = It was 20.14, that is, 20.1% by volume.

[Production of volume hologram recording medium]
A 10 μm thick aluminum foil is placed as a spacer on the top, bottom, left, and right ends of the slide glass, and the volume hologram recording material composition is dropped onto the center of the slide glass (the region sandwiched between 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.

[Measurement of physical properties during volume hologram recording]
The volume hologram recording medium of the present invention was subjected to two-beam interference exposure using the apparatus shown in FIG. ^Two- beam interference exposure (grating spacing 1 μm) was performed on the volume hologram recording medium with an exposure power density of 250 mW / cm ² using an Nd: YVO ₄ laser with a wavelength of 532 nm. The light emitted from the Nd: YVO ₄ laser is divided into two by a half mirror through a beam expander, and each volume is irradiated to a volume hologram recording medium, and interference fringes of both lights are recorded to form a volume hologram. .
At the same time, the volume hologram recording medium is irradiated with a helium-neon (He-Ne) laser with a wavelength of 632.8 nm, which is not exposed to light, and the hologram formation process is monitored and detected by detecting the diffracted light with a photodetector. Efficiency was evaluated. Further, the angle dependency of the diffraction efficiency after exposure was measured, and the film thickness after exposure of the sample was calculated. Furthermore, the exposure time change of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn _sat ) were evaluated from the obtained diffraction efficiency and film thickness. The results are shown in Table 1. FIG. 4 shows changes in Δn with respect to the exposure time.

<Example 2>
A sample having a volume fraction of 12.2% by volume of HB-TmDA40 was prepared in the same manner as in Example 1, and the change in exposure time of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn _sat ) were evaluated. did. The results are shown in Table 1. FIG. 5 shows changes in Δn with respect to the exposure time.

<Example 3>
A sample having a volume fraction of 15.6% by volume of HB-TmDA40 was prepared in the same manner as in Example 1, and the change in exposure time of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn _sat ) were evaluated. did. The results are shown in Table 1. FIG. 6 shows the change of Δn with respect to the exposure time.

<Example 4>
A sample having a volume fraction of 17.9% by volume of HB-TmDA40 was prepared in the same manner as in Example 1, and the change in exposure time of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn _sat ) were evaluated. did. The results are shown in Table 1. FIG. 7 shows changes in Δn with respect to the exposure time.

<Example 5>
A sample having a volume fraction of 22.9% by volume of HB-TmDA40 was prepared in the same manner as in Example 1, and the change in exposure time of the refractive index modulation amount (Δn) and the saturated refractive index modulation amount (Δn _sat ) were evaluated. did. The results are shown in Table 1. FIG. 8 shows the change of Δn with respect to the exposure time.

<Comparative example>
A sample in which HB-TmDA40 was not dispersed was prepared in the same manner as in Example 1, and the change in exposure time of the refractive index modulation amount (Δn) was evaluated. FIG. 9 shows changes in Δn with respect to the exposure time.

Samples with different volume fractions of the HB-TmDA40 produced in Example 1 to Example 5 (12.2 vol%, 15.6 vol%, 17.9 vol%, 20.1 vol%, 22.9 vol) %), The dependency of Δn _sat on the concentration of HB-TmDA40 was evaluated. FIG. 10 shows Δn _sat with respect to the volume fraction (volume%) of HB-TmDA40.

[Table 1]

As shown in Table 1, the saturation refractive index modulation amount Δn _sat of the volume hologram recording material composition of the present invention is extremely high, and Δn _sat tends to increase as the volume fraction of the fine particles (HB-TmDA40) increases. (See FIG. 10).
On the other hand, as shown in FIG. 9, when recording a volume hologram in the same manner as in the Example (Comparative Example) on a medium to which fine particles (HB-TmDA40) are not added, the diffraction efficiency once rises but the passage of time. As a result, it decreased rapidly and eventually disappeared. Since this is a single component of a functional monomer, it corresponds to the loss of refractive index modulation when polymerized as a whole.

  The composition for volume hologram recording material of the present invention and the volume hologram recording medium obtained from them can be used for three-dimensional image display, large-capacity memory for images and bit information, diffractive optical elements, and the like.

DESCRIPTION OF SYMBOLS 1 Hologram recording medium 2 Nd: YVO ₄ laser 3 Beam expander 4 He-Ne laser 5, 6, 7, 8, 9, 10, 11 Mirror 12 Beam sampler 13 Half mirror 14, 15 Half wavelength plate 16, 17 Polarizing prism 18, 19, 20 Photodetector

Claims (9)

A composition for a volume hologram recording material used for forming a pattern by pattern exposure,
(A) polymerizable compound (however, does not include (d) described later) ,
(B) a photopolymerization initiator,
(C) a triazine ring-containing hyperbranched polymer and (d) a vinyl monomer having an ether structure (excluding a (meth) acrylic monomer having an ether structure described later) and / or a (meth) acrylic monomer having an ether structure, And a composition for a volume hologram recording material comprising a vinyl monomer having an amide structure (excluding a (meth) acrylic monomer having an amide structure described below) and / or a (meth) acrylic monomer having an amide structure . Wherein (a) the polymerizable compound (d) vinyl monomers having an ether structure (excluding (meth) acrylic monomers having an ether structure described below.) And / or having an ether structure (meth) acrylic monomer, and A refractive index of a polymer with a vinyl monomer having an amide structure (excluding a (meth) acrylic monomer having an amide structure described below) and / or a (meth) acrylic monomer having an amide structure ; and (c) triazine The composition for a volume hologram recording material according to claim 1, wherein the difference from the refractive index of the ring-containing hyperbranched polymer is 0.01 or more and 0.6 or less. Wherein (a) a polymer of a polymerizable compound, wherein (c) a triazine ring-containing hyperbranched polymers and the (d) vinyl monomers having an ether structure (where having an ether structure below (meth) excluding acrylic monomer.) And / or a (meth) acrylic monomer having an ether structure, and a vinyl monomer having an amide structure (except for a (meth) acrylic monomer having an amide structure described later) and / or a (meth) acrylic monomer having an amide structure. 3. The composition for volume hologram recording material according to claim 1, wherein a proportion of the (c) triazine ring-containing hyperbranched polymer in a total volume of the polymer is 3 volume% or more and 50 volume% or less. object. The composition for a volume hologram recording material according to any one of claims 1 to 3 , wherein the pattern exposure is interference exposure, and is used for forming a hologram by the interference exposure. The volume hologram recording layer containing the composition for volume hologram recording materials of any one of Claims 1 thru | or 4 . A volume hologram recording medium comprising the volume hologram recording layer according to claim 5 . The volume hologram recording medium according to claim 6 , wherein the volume hologram recording layer has a structure in which each has a flat surface and is disposed between two transparent substrates facing each other. A pattern comprising the steps of coating the volume hologram recording material composition according to any one of claims 1 to 4 on a support to form a coating film, and pattern exposing the coating film. Forming method. The pattern forming method according to claim 8 , wherein the pattern exposure is interference exposure.