JPWO2020050321A1 - Composition for Volume Hologram Recording Material Containing Triazine Ring-Containing Hyperbranched Polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for a volume hologram recording material capable of permanently forming a hologram having extremely low light scattering loss and high diffraction efficiency, and a hologram recording medium using the composition. A composition for a volume hologram recording material used for forming a pattern by pattern exposure, which is different from the (a) (meth) hydroxyalkyl acrylate and (b) (a) components. A composition for a volumetric hologram recording material containing a compound, (c) a triazine ring-containing hyperbranched polymer and (d) a photopolymerization initiator, and a hologram recording medium using the composition. [Selection diagram] None

Description

According to the present invention, 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 the spatial distribution of each component is changed, and a pattern using the composition. Regarding the formation method. The present invention also relates to a volume hologram recording layer containing the composition for the hologram recording material and a volume hologram recording medium including 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. 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, and head-up displays. These application fields usually require a large change in refractive index and high recording sensitivity.

As a conventional composition for a typical hologram recording material, a gelatin dichromate photosensitive material and a bleached silver salt photosensitive material have been used. Although these have high diffraction efficiency, they have a drawback that the processing at the time of creating a hologram is complicated and a wet development processing is particularly required.
DuPont's Omnidex series is widely known as a dry hologram photosensitive material that overcomes these drawbacks. This material contains a radical polymerization monomer and a binder polymer, a photoradical polymerization initiator and a sensitizing dye as main components, and records a hologram by utilizing the 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 formed accordingly, and radicals are formed from a portion where light is weak to a portion where light is strong. Diffusion movement of the polymerization monomer occurs. As a result, the density of the radical polymerization monomer and the density of the polymerized polymer can be sparse depending on the intensity of the interference light, and a hologram is formed as the difference in the refractive index between them and the binder polymer. Although this material system has high performance as a photopolymer for holograms currently reported, it has been pointed out that the thickness is limited to about 30 μm, and that there are problems in heat resistance and transparency.

Further, a material system in which radical polymerization and cationic polymerization are used in combination (see Patent Document 1) and a material system in which cationic polymerization is used (see Patent Document 2) have been reported. Since they are incompatible 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 due to the decrease in transparency. Moreover, it is still inadequate in terms of mechanical strength and environmental stability.

Further, a material system in which an inorganic substance network and a photopolymerizable monomer are used in combination is disclosed (see Patent Document 3). When an inorganic material that can form a network is used as a binder, it 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 brittle, has problems of inferior flexibility, processability, and coating suitability, and the compatibility between the inorganic binder and the organic monomer is poor, and it is necessary to prepare a uniform coating material. There is a problem of difficulty.

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 the present invention, it is necessary to give the matrix fluidity, and not only the solidity is poor, but also the interface adhesion between the metal particle interface and the solid matrix is poor, it is brittle, and water penetrates into the interface. be.

Further, a hologram recording material using an organic-inorganic hybrid polymer and organic metal 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, which poses 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).
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.

Japanese Unexamined Patent Publication No. 5-107999 U.S. Pat. No. 5,579,721 Japanese Unexamined Patent Publication No. 6-019040 Special Table 2000-5087883 JP-A-2002-236440 Japanese Unexamined Patent Publication No. 2003-084651 Japanese Unexamined Patent Publication No. 2005-099612 Japanese Unexamined Patent Publication No. 2010-250246 Japanese Unexamined Patent Publication No. 2014-197191

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

The present invention uses a triazine ring-containing hyperbranched polymer having low cohesiveness and an extremely high refractive index as fine particles in a volume hologram recording material, and (meth) acrylic as a component capable of dispersing and dissolving the hyperbranched polymer. A composition for a volumetric hologram recording material capable of permanently forming a hologram having extremely low light scattering loss and high diffraction efficiency by blending hydroxyalkyl acid acid together with other polymerizable components, and hologram recording using the composition. The purpose is to provide a medium.

The present inventors have found the present invention as a result of diligent studies to achieve the above object.
That is, as a first aspect, it is a composition for a volume hologram recording material used for forming a pattern by pattern exposure.
(A) (Meta) hydroxyalkyl acrylate,
(B) A polymerizable compound different from the component (a),
The present invention relates to a composition for a volume hologram recording material containing (c) a triazine ring-containing hyperbranched polymer and (d) a photopolymerization initiator.
As a second aspect, 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. It relates to the composition for a volume hologram recording material according to 1 viewpoint.
As a third aspect, the composition for a volume hologram recording material according to the first aspect or the second aspect, wherein the pattern exposure is an interference exposure and is used for forming a hologram by the interference exposure.
As a fourth aspect, the volume hologram recording material according to any one of the first to third aspects, wherein the polymerizable compound different from the components (b) and (a) is a polyfunctional (meth) acrylate. Regarding the composition.
As a fifth aspect, the present invention relates to a volume hologram recording layer containing 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.
A seventh aspect is the volume hologram recording medium according to the sixth aspect, wherein the volume hologram recording layer has a structure in which each has a plane and is arranged between two transparent substrates facing the planes.
As an eighth viewpoint, a step of applying the composition for a volume hologram recording material according to any one of the first to fourth viewpoints to a support to form a coating film, and pattern exposure to the coating film. It relates to a method of forming a pattern including a step.
As a ninth aspect, the method for forming a pattern according to the eighth aspect, wherein the pattern exposure is interference exposure.

According to the present invention, as fine particles, a triazine ring-containing hyperbranched polymer having low cohesiveness and an extremely high refractive index is dispersed together with hydroxyalkyl (meth) acrylate in a polymerizable component such as another polymerizable compound. It is possible to provide a composition for a volumetric hologram recording material capable of permanently forming a hologram having low light scattering loss and high diffraction efficiency, and a volumetric hologram recording medium.

^{FIG. 1 is a diagram showing a 1} H NMR spectrum of HB-TmDA obtained in Production Example 1. FIG. 2 is a volume hologram recording device (recording / reproducing wavelength 532 nm) used in the examples. FIG. 3 shows the refractive index modulation with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Example 1 ((a) component: 4HBA, volume fraction of HB-TmDA: 19.6% by volume). It is a figure which shows the change of the quantity Δn. FIG. 4 shows the refractive index modulation with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Comparative Example 1 ((a) component: THFA + NVP, volume fraction of HB-TmDA: 19.9% by volume). It is a figure which shows the change of the quantity Δn. FIG. 5 is a diagram showing a change in the refractive index modulation amount Δn with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Example 2 (volume fraction of HB-TmDA: 15.1% by volume). Is. FIG. 6 is a diagram showing a change in the amount of refractive index modulation Δn with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Example 3 (volume fraction of HB-TmDA: 20.0% by volume). Is. FIG. 7 is a diagram showing a change in the amount of refractive index modulation Δn with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Example 4 (volume fraction of HB-TmDA: 23.0% by volume). Is. FIG. 8 is a diagram showing a change in the amount of refractive index modulation Δn with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Example 5 (volume fraction of HB-TmDA: 25.0% by volume). Is. FIG. 9 is a volume hologram recording device (recording / reproducing wavelength 640 nm) used in the examples. FIG. 10 is a diagram showing a change in the amount of refractive index modulation Δn with respect to the exposure time (seconds) obtained by using the volume hologram recording medium of Example 6 (volume fraction of HB-TmDA: 20.1% by volume). Is.

The composition for volumetric hologram recording material of the present invention comprises (a) (meth) hydroxyalkyl acrylate, (b) (a) a polymerizable compound different from the components, (c) a triazine ring-containing hyperbranched polymer, and (d). It is composed of a photopolymerization initiator.
Hereinafter, each component contained in the composition for a volume hologram recording material of the present invention will be described.

[(A) (Meta) hydroxyalkyl acrylate]
The hydroxyalkyl (a) (meth) acrylate in the present invention can disperse the (c) triazine ring-containing hyperbranched polymer described later, and is a polymerizable compound different from the components (b) (a) described later. On the other hand, it functions as a component that can be dispersed together with the component (c).
In the present specification, (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 compound is substituted with at least one hydroxy group in the (meth) acrylic acid alkyl ester compound, and the alkyl group is two or more hydroxy groups. It may be a compound substituted with, or may be a compound substituted with another substituent.
Among them, as the component (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, for example, the alkyl group is 1. Monohydroxyalkyl (meth) acrylate substituted with only one hydroxy group can be used.

Examples of the component (a) include (meth) acrylic acid ester 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 and a hydroxynonyl group. , Hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group, hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, hydroxyheptadecyl group, hydroxyoctadecyl group, hydroxynonadecil group and hydroxyeico A sill group can be mentioned. These hydroxyalkyl groups may be linear, branched, cyclic, or a combination thereof.

Specific examples of the component (a) above 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) acrylic Hydroxynonyl acid, hydroxydecyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, hydroxyundecyl (meth) acrylate, hydroxydodecyl (meth) acrylate (sometimes referred to as hydroxylauryl (meth) acrylate) ), (Meta) hydroxytridecyl acrylate, (meth) hydroxytetradecyl acrylate, (meth) hydroxypentadecyl acrylate, (meth) hydroxyhexadecyl acrylate, (meth) hydroxyheptadecyl acrylate, (meth) ) Hydroxyoctadecyl acrylate, (meth) hydroxynonadecil acrylate, (meth) hydroxyeicosyl acrylate, glycerin mono (meth) acrylate, 1,1,1-trimethylol propane mono (meth) acrylate, pentaerythritol mono ( Meta) acrylate and the like can be mentioned. These may be 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), which will be described later, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic 2-Hydroxy-1-methylethyl acid, 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, and (meth) acrylate is preferable. ) 4-Hydroxybutyl acrylate is more preferred.

The blending amount of hydroxyalkyl (a) (meth) acrylate in the composition for volumetric hologram recording material of the present invention is 0.1 to 1, 1 part by mass with respect to 1 part by mass of a polymerizable compound different from the components (b) and (a). It is 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) Polymerizable compound different from 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 that are polymerized by the action of the photopolymerization initiator, and the component (a). : There is no particular limitation as long as it is a compound different from hydroxyalkyl (meth) acrylate. Examples of the polymerizable moiety include an ethylenically unsaturated bond, which is a radically 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, and the like. It also includes oligomers and reactive polymers.

Examples of such a polymerizable compound include compounds having a radically polymerizable moiety or a cationically polymerizable moiety.
Examples of the polymerizable compound having a radically polymerizable moiety include a compound having an ethylenically unsaturated bond. Further, examples of the polymerizable compound having a cationically polymerizable moiety include a compound having a vinyl thioether structure or a cyclic ether structure such as an epoxy ring or an oxetane ring.

<Polymerizable compound with radically 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. Esther compounds with; ester compounds obtained by esterification of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polyvalent carboxylic acids; and alkylene oxide modification of these. Examples thereof include compounds (ethylene oxide modified products, propylene oxide modified products, etc.).

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

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 isobolonyl acrylate. .. Further, a methacrylic acid ester compound in which the acrylate moiety of these exemplified compounds is replaced with methacrylate, an itaconic acid ester compound in which itaconate is replaced, a crotonic acid ester compound in which crotonate is replaced, a maleic acid ester compound in which maleate is replaced, and the like are also available. Can be mentioned.

Specific examples of the ester compound of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethyl propantriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol. Examples thereof include acrylic acid ester compounds such as triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol polyacrylate. In addition, a methacrylic acid ester compound in which the acrylate moiety of these exemplified compounds is replaced with methacrylate, an itaconic acid ester compound in which itaconate is replaced, a crotonic acid ester compound in which crotonate is replaced, a maleic acid ester compound in which maleate is replaced, and the like are also mentioned. Be done.

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.

The ester compound obtained by the 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 compound, but is typical. Specific examples include a condensate of acrylic acid and phthalic acid and ethylene glycol, a condensate of acrylic acid and maleic acid and diethylene glycol, a condensate of methacrylic acid and terephthalic acid and pentaerythritol, acrylic acid and adipic acid. Examples thereof include a condensate of butanediol and glycerin.

In addition to the above ester compounds, as a compound having an ethylenically unsaturated bond, a urethane compound 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 thereof include compounds that can be obtained by reacting with an acid ester. Examples of the urethane compound include EBECRYL (registered trademark) series urethane acrylate manufactured by Daicel Cytec Co., Ltd. Specifically, by using EBECRYL8301 or the like, it is excellent 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.

In the present invention, as the compound having an ethylenically unsaturated bond, an acrylic acid ester compound and a methacrylic acid ester compound, and their alkylene oxide modified products (ethylene oxide modified product, propylene oxide modified product, etc.) can be particularly preferably used. .. Among them, polyfunctional (meth) acrylic acid ester compounds which are ester compounds of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and their alkylene oxide modified products (ethylene oxide modified products, propylene oxide modified products, etc.) are preferred examples. Can be mentioned.
These compounds having an ethylenically unsaturated bond may be used alone or mixed as necessary.

<Polymerizable compound with 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, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, adipate diglycidyl ester, o-phthalic acid diglycidyl ester , Dibromophenyl glycidyl ether, 1,2,7,8-diepoxy octane, 1,6-dimethylol perfluorohexane diglycidyl ether, 4,4'-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl 3', 4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxylane, 2- (3,4-epoxycyclohexyl) -3', 4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxybis (3,4-epoxycyclohexylmethane), 4', 5'-epoxy-2'-methyl Cyclohexylmethyl4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol bis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether And so on.

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 cationically polymerizable sites may be used alone or mixed as necessary.

<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.
Further, as the component (b), a compound having one polymerizable moiety and a compound having two or more polymerizable moieties (bifunctional or higher polymerizable compound) may be used in combination. When a compound having one polymerizable site and a compound having two or more polymerizable sites are used in combination, the (c) triazine ring-containing hyperbranched polymer, which will be described later, is rapidly diffused, and characteristics such as diffraction efficiency become a more preferable form. There is expected.
When a bifunctional or higher functional compound is used as the component (b), the amount (mass) used is 10 times the total mass of the composition excluding the bifunctional or higher polymerizable compound. Up to (mass) is preferable. If the amount of the bifunctional or higher-functional polymerizable compound used is larger than this ratio, the amount of dispersion of the (c) triazine ring-containing hyperbranched polymer is relatively small, and good properties such as diffraction efficiency may not be obtained. Keep in mind the point.
Examples of the bifunctional or higher-functional polymerizable compound include the above-mentioned polymerizable compounds having a radically polymerizable moiety or a compound having a cationically polymerizable moiety, which has two or more polymerizable moieties.
Further, as a polymerizable compound different from the components (b) and (a) above, it is particularly preferable to use a polyfunctional (meth) acrylate and a modified alkylene oxide thereof.

[(C) Triazine ring-containing hyperbranched polymer]
The composition for volumetric hologram recording material of the present invention contains (c) a triazine ring-containing hyperbranched polymer as an essential component.
The blending amount of the component (c) contained in the composition for volume hologram recording material of the present invention is the amount of the component (c) in 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, and more preferably 15% by volume or more and 50% by volume or less.

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.

In the above formula (1), R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.

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 that the heat resistance of the polymer is further enhanced, the number of carbon atoms is 1. It is more preferably 10 to 10, and even more preferably 1 to 3. The structure may be linear, branched or cyclic.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group and 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 group, 1-ethylpropyl group, cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclo Propyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1- Dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2 -Ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, 1-methyl Cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethylcyclobutyl group, 2-ethylcyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethyl Cyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-propylcyclopropyl group, 2-propyl Cyclopropyl group, 1-isopropylcyclopropyl group, 2-isopropylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group , 1-Ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group and the like.

The number of carbon atoms of the alkoxy group is not particularly limited, but the number of carbon atoms is preferably 1 to 20, and in consideration of further enhancing the heat resistance of the polymer, the number of carbon atoms is 1 to 10. It is more preferable that there is, and it is even more preferable that it is 1 to 3. Further, the structure of the alkyl portion may be linear, branched or cyclic.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group and 1-methyl. Butoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 1-ethylpropoxy group, n-hexyloxy group , 1-Methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethyl Butoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 3,3-dimethylbutoxy group, 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 group and the like.

The number of carbon atoms of the aryl group is not particularly limited, but it is preferably 6 to 40, and considering that the heat resistance of the polymer is further enhanced, the number of carbon atoms is 6 to 16. It is more preferable that there is, and it is even more preferable that there is 6 to 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. 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 thereof include a 9-anthryl group, a 1-phenyl group, a 2-phenyl group, a 3-phenyl group, a 4-phenyl group, a 9-phenyl group and the like.

The number of carbon atoms of the aralkyl group is not particularly limited, but the number of carbon atoms is preferably 7 to 20, and the alkyl portion thereof may be linear, branched chain, or cyclic.
Specific examples thereof include a benzyl group, a p-methylphenylmethyl group, an m-methylphenylmethyl group, an o-ethylphenylmethyl group, an m-ethylphenylmethyl group, a p-ethylphenylmethyl group and a 2-propylphenylmethyl group. , 4-Isobutylphenylmethyl 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 have a branched structure of a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, and the number of carbon atoms 1 to 10 independently of each other. It represents a good 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. Representing an alkyl group which may be represented, W ¹ and W ² are independent of each other and are single-bonded, CR ⁹⁵ R ⁹⁶ (in the formula, R ⁹⁵ and R ⁹⁶ are independent of each other and have 1 hydrogen atom or 1 carbon atom. Represents an alkyl group which may have a branched structure of 10 to 10 (where R ⁹⁵ and R ⁹⁶ may form a ring together with the carbon atom to be bonded), C = O. , O, S, SO, SO ₂ or NR ⁹⁷ (in the formula, R ⁹⁷ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms).
Examples of these alkyl groups and alkoxy groups include groups similar to those mentioned above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

（式中、Ｒ^９８〜Ｒ^１０１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、Ｙ^１及びＹ^２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。Further, in the above formula, X ¹ and X ² are independent of each other and may have a single bond, a branched structure having 1 to 10 carbon atoms, or an alkylene group of the formula (14).

(In the formula, R ^{98 to} R ¹⁰¹ are independent of each other and may have a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or a carbon atom. Representing an alkoxy group which may have a branched structure of the number 1 to 10, Y ¹ and Y ² may have a single bond or a branched structure of 1 to 10 carbon atoms independently of each other. Represents an alkylene group.)
Represents a group represented by.
Examples of these halogen atoms, alkyl groups, and alkoxy groups include groups similar to those mentioned 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 and a pentamethylene group.

Suitable Ar in the formula (1) in the present invention includes at least one selected from the groups represented by the formulas (2), (5) to (13), and the formulas (2) and (5). , (7), (8), 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 formulas, but are not limited thereto.

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

（式中、Ｒ、Ｒ’及びＲ^１〜Ｒ^４は、前記と同じ意味を表す。）Among them, as a suitable repeating unit structure contained in (c) a triazine ring-containing hyperbranched polymer, Ar is a divalent group represented by the formula (2) in the repeating unit structure represented by the formula (1). Some, that is, the repeating unit structure represented by the following formula (15) is preferable.

(In the formula, R, R'and ^{R 1 to R 4} have the same meanings as described above.)

A particularly suitable 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 most suitable. be.

（式中、Ｒ及びＲ’は、上記と同じ意味を表す。）

(In the formula, R and R'have the same meaning as above.)

The weight average molecular weight of the (c) triazine ring-containing hyperbranched polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, and further improving heat resistance. From the viewpoint of lowering the shrinkage rate, 2,000 or more is preferable, and from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution, 50,000 or less is preferable, and 30,000 or less is more preferable. , Further preferably 10,000 or less.
The weight average molecular weight in the present invention is the average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.

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

（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。）

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

[(D) Photopolymerization Initiator]
The photopolymerization initiator in the present invention has a function of initiating the polymerization of a polymerizable compound different from the component (a) and / or the component (b): component (a) by pattern exposure described in detail later. There is no particular limitation as long as it is a compound having.
Component (b): When a compound having an ethylenically unsaturated bond, which is a radically polymerizable site, is used as a polymerizable compound different from the component (a), the photopolymerization initiator is basically a pattern exposure. Sometimes a photoradical polymerization initiator that produces active radicals is used.
Further, when a compound having a vinyl ether structure, an epoxy ring or an oxetane ring, which is a cationically polymerizable site, is used as a polymerizable compound different from the component (b): component (a), the photopolymerization initiator may be used. Basically, a photoacid generator that produces Lewis acid or Bronsted acid during pattern exposure is used.

<Photoradical polymerization initiator>
The photoradical polymerization initiator is not particularly limited as long as it is a compound that generates an active radical during pattern exposure, and is, for example, a benzoin compound, an α-aminoalkylphenone compound, an N-aryl-α-amino acid compound, or a thioxanthone. System compounds, azo compounds, azide compounds, diazo compounds, o-quinone diazide compounds, acylphosphine oxide compounds, oxime ester compounds, organic peroxides, benzophenones, biscmarin, bisimidazole compounds, titanosen 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 in combination of two or more as required.

The titanosen compound is not particularly limited, but for example, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) diphenyltitanium, and 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 (methylcyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (2,6-difluorophenyl) bis (methylcyclo) Examples thereof include pentadienyl) titanium, bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.

The N-aryl-α-amino acid-based compound is not particularly limited, and is, 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-phenylglycine, N-phenylalanine, N- (p-acetylphenyl) alanine, N- (m-acetylphenyl) alanine, etc. Can be mentioned.

The trichloromethyltriazine-based compound is not particularly limited, but 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-phenyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine And so on.

Examples of benzoin compounds include benzoin ethyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropane-1-. It can be turned on and the like.

Examples of the α-aminoalkylphenone compound include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino). Phenyl) butane-1-one and the like can be mentioned.

Examples of the thioxanthone compound 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-Methylpropion amidine), 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-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-tetrahydropyrimidine-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 can be mentioned.

Examples of the azide compound include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4'-diazide chalcone, 4,4'-diazidodiphenyl sulfide, 2 , 6-Bis (4'-Azidobenzal) -4-methylcyclohexanone, 4,4'-Diazidosylben and the like.

Examples of the diazo compound include 2,5-diethoxy-4-p-tolylmercaptobenzenediazonium tetrafluoroborate, 4- (dimethylamino) benzenediazonium chloride, 4- (diethylamino) benzenediazonium tetrafluoroborate and the like. can.

Examples of the o-quinone diazide compound include 1,2-naphthoquinone diazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinone diazide (2) -5-sulfonic acid ester, and 1,2-naphthoquinone diazide (2). ) -4-sulfonyl chloride and the like.

Examples of the acylphosphine oxide compound include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.

Examples of the oxime ester compound include 2- (O-benzoyloxime) -1- (4- (phenylthio) phenyl) -1,2-octanedione and 1- (O-acetyloxime) -1- (9-ethyl). -6- (2-Methylbenzoyl) -9H-carbazole-3-yl) esterone and the like can be mentioned.

Examples of benzophenones include benzophenone, 4,4'-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacrydone, 2-benzoylnaphthalene, 4-benzoylbiphenyl and 4-benzoyl. Examples thereof include diphenyl ether, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and the like.

Examples of the bisque marine include 3,3'-carbonylbis (7-diethylaminocoumarin), which is commercially available as BC (CAS [63226-13-1]) by Midori Kagaku 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. 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.

The boron compound is not particularly limited, but for example, trialkylborones such as triethylboron, tripropylboron, tributylboron, trihexylboron, and tricyclohexylboron; triarylborones such as triphenylboron and trinaphthylboron. Alkoxydialkylborates such as ethoxydiethylboron, propoxydipropylboron, butoxydibutylborate; and alkyltriarylborate (butyltriphenylborate, butyltrinaphthylborate, etc.), dialkyldiarylborate (dibutyldiphenylborate, dibutyldinaphthyl) Metal salts (lithium, sodium, potassium, magnesium, etc.), ammonium salts (tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.) of borates such as borate (borate, etc.) and trialkylaryl borate (tributylphenyl borate, tributylnaphthylborate, etc.) ), Pyridinium salt (methylpyridinium, ethylpyridinium, butylpyridinium, etc.), quinolinium salt (methylquinolinium, ethylquinolinium, butylquinolinium, etc.), phosphonium salt, sulfonium salt and the like.

Among these photoradical polymerization initiators, titanosen compounds, N-aryl-α-amino acid compounds, and trichloromethyltriazine compounds are preferable. Further, among the titanosen compounds, bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium is used, and among the N-aryl-α-amino acid compounds, N- Among the trichloromethyltriazine compounds, 2,4,6-tris (trichloromethyl) -1,3,5-triazine can be mentioned as a preferable example of phenylglycine. N-phenylglycine may be used in combination with a sensitizer such as rose bengal or 3,3'-dipropylthiadicarbocyanine iodide, which will be described later, and 2,4,6-tris (trichloromethyl)-. 1,3,5-triazine may be used in combination with a sensitizer such as 3,3'-dipropylthiadicarbocyanine iodide described later.

<Photoacid generator>
The photoacid generator is not particularly limited as long as it is a compound that produces Lewis acid or Bronsted acid during pattern exposure, but for example, onium salt compounds such as diallyl iodonium salt compound, triarylsulfonium salt compound, and 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 of iodoniums such as 4- (2-methylpropyl) phenyl) iodonium and 3,3'-dinitrophenyl iodonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.

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). ) Tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like of sulfonium such as sulfonium can be mentioned.

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

These photopolymerization initiators such as a photoradical polymerization initiator and a photoacid generator may be used alone, or two or more thereof may be mixed and used as required.
The blending amount of the photopolymerization initiator in the composition for volumetric hologram recording material of the present invention is 0.01 with respect to the total amount of the polymerizable compound different from the component (a) and the component (b): component (a). It is 10% by mass, preferably 0.05 to 5% by mass.

[Volume hologram recording medium]
The present invention also covers a volume hologram recording layer containing a composition for a volume hologram recording material containing the above components (a) to (d), and a volume hologram recording medium including the recording layer.
In addition to the above 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, if necessary. May be good.

For example, the 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-pentamethylpyromethene-BF ₂ complex, _{1,3,5,7,8-pentamethylpyromethene-BF 2} Pyromethene complex compounds such as complexes; xanthene dyes such as eosin, ethyleosin, erythrosin, fluorescein, rosebengal; 3,3'-diethyloxacarbocyanine iodide, 3,3'-diethylthiacarbocyanine iodide, 3, 3'-diethyloxadicarbocyanine iodide, 3,3'-dipropylthiadicarbocyanine 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] squaline, 2,4-bis [8-hydroxy-1,1,7,7-tetramethylduro Squalium dyes such as lysine-9-yl] squaline; 1- (1-methylnaphtho [1,2-d] thiazole-2 (1H) -iriden) -4- (2,3,6,7-tetrahydro-1H) , 5H-benzo [ij] quinolidine-9-yl) -3-buten-2-one, 1- (3-methylbenzothiazole-2 (3H) -iriden) -4- (p-dimethylaminophenyl) -3 Ketothiazolin compounds such as -buten-2-one; 2- (p-dimethylaminostyryl) -naphtho [1,2-d] thiazole, 2- (4- (p-dimethylaminophenyl) -1,3-butadienyl) Examples thereof include styryl or phenylbutadienyl heterocyclic compounds such as naphthol [1,2-d] thiazole. In addition, 2,4-diphenyl-6- (p-dimethylaminostyryl) -1,3,5-triazine, 2,4-diphenyl-6-((2,3,6,7-tetrahydro-1H, 5H-) Benzo [ij] quinolidine-9-yl) -1-ethen-2-yl) -1,3,5-triazononanthrill = (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] Kinolidine-9-yl) -1-ethen-2-yl-ketone, 2,5-bis (p-dimethylaminocinnamylidene) cyclopentanone, 5,10,15,20-tetraphenylporphyrin and the like can be mentioned. .. When a sensitizer is used, the amount of the sensitizer added is, for example, 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass with respect to 1 part by mass of the (d) photopolymerization initiator. be.

Further, a binder resin may be added as a binder in order to maintain the uniformity of the film thickness and to allow the interference film formed by the polymerization by light irradiation to exist stably.
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) resins. ) Acrylate alkyl ester copolymer, vinyl chloride and acrylonitrile copolymer, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinylpyrrolidone, ethyl cellulose, acetyl cellulose and the like can be mentioned.

In order to prepare 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 together with a sensitizer, a binder resin and the like, if necessary. As it is, it is applied on a transparent substrate (support) without solvent, or a mixture thereof is added with a solvent or an additive to form a so-called varnish, which is applied on the transparent substrate, dried, and then on the transparent substrate. A recording medium formed by a volumetric hologram recording layer 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 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 in the components used and gives good coating properties, but for example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and the like. Cellosolve-based solvent; propylene glycol-based solvent 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; Ester solvents such as butyl acetate, amyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate; butanol, Alcohol-based solvents such as hepthanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketone solvents such as methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Examples thereof include amide-based solvents such as 2-pyrrolidone; or mixed solvents thereof, and those to which aromatic hydrocarbons are added.
When the above solvent is used, the ratio of the amount used is usually in the range of about 1 to 20 times by mass ratio with respect to the total amount of the material composition for volume hologram 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 rotary coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used.

As the protective layer, a known technique for preventing adverse effects such as deterioration of sensitivity and storage stability due to oxygen, for example, coating of a water-soluble polymer or the like can also be used.

The present invention also covers a pattern forming method using the composition for volume hologram recording material.
That is, it 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 preferable.
As the support, those listed as the above-mentioned transparent substrate can be preferably used, and as the coating method on the support, the above-mentioned coating method on the transparent substrate can be mentioned.

As described above, conventionally, as a volume hologram recording composition, a composition composed of a plurality of functional monomers having different refractive indexes, a composition composed of a liquid organic substance and a functional monomer, and the like are known. In order to obtain a hologram having high diffraction efficiency using such a composition, it is necessary to increase the difference in refractive index between the region corresponding to the bright part and the region corresponding to the dark part of the interference fringes. However, since the refractive index of organic substances that has been conventionally proposed is usually limited to about 1.3 to 1.6, it is said that there is a limit to increasing the difference in refractive index with a hologram recording material made of a combination of organic substances. rice field.
The triazine ring-containing hyperbranched polymer used in the present invention has a high refractive index exceeding 1.7, and therefore, the difference in refractive index is large even in combination with an organic substance (resin component, etc.), which has been considered to have a limit in the past. Therefore, a hologram having a high refractive index can be obtained.

The recording principle of the volume hologram in the volume hologram recording medium using the composition for the 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 by utilizing the difference in the refractive index of at least two kinds of components contained in the recording layer due to mutual diffusion of interference fringes into bright and dark areas. Therefore, under the conditions of pattern exposure for forming a pattern (for example, the 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 properties It is important that the difference between the refractive index of the polymer generated from the polymerizable component such as a compound and the refractive index of the triazine ring-containing hyperbranched polymer is large.

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 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 sex component is large, and for example, the difference is preferably 0.01 to 0.6. Further, it can be said that the difference in refractive index is more preferably 0.02 to 0.5 or 0.03 to 0.4. Generally, the refractive index of the (meth) acrylate-based polymer is 1.49 to 1.53, and the refractive index of the epoxy-based polymer is 1.55 to 1.61. From this point of view, the above-mentioned components, that is, the suitable (c) triazine ring-containing hyperbranched polymer used in the present invention, and the polymerizable component (particularly, (b) polymerization different from hydroxyalkyl (meth) acrylate). Sex compounds) will be selected respectively.
The triazine ring-containing hyperbranched polymer has a relatively high refractive index, and for example, the refractive index for light having a wavelength of 589 nm may exceed 1.7. Therefore, the refractive index of the polymer produced from the polymerizable component (hydroxyalkyl (meth) acrylate and a polymerizable compound different from the hydroxyalkyl (meth) acrylate) used in the present invention is preferably relatively small compared to the above values. For example, a polymerizable component that gives a polymer having a refractive index of 1.3 or more and 1.7 or less 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.

The refractive index of the polymer is determined by applying a composition composed of a polymerizable component and a photopolymerization initiator on the support, drying it if necessary, and then using light for interference exposure for hologram recording. It can be obtained by subjecting the composition to spatially uniform exposure under the conditions used to obtain a polymer, 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 ((meth) acrylic) suitable for the composition for hologram recording material of the present invention. (Hydroxyalkyl acid and other polymerizable compounds, etc.) and triazine ring-containing hyperbranched polymers can be selected, respectively.

Hereinafter, the present invention will be described in more detail 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 analysis of physical properties are as follows.
[ ^{1 1} H NMR]
Equipment: NMR System 400NB manufactured by Agilent Technologies, Inc.
Measuring solvent: DMSO-d ₆
Reference substance: Tetramethylsilane (δ0.00ppm)
[GPC (Gel Permeation Chromatography)]
Equipment: HLC-8200GPC manufactured by Tosoh Corporation
Column: Showa Denko Corporation Shodex (registered trademark) GPC KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: THF
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [membrane density]
Equipment: Multipurpose X-ray diffractometer manufactured by Bruker Japan Co., Ltd. D8 DISCOVER
Tube voltage-current: 50kV-100mA
Measurement range: 0.2-3.000 deg (2θ)
Step width: 0.005 deg (2θ)
time / step: 0.5 seconds / step
[5% weight loss temperature (Td _5% )]
Equipment: Differential thermal balance (TG-DTA) TG-8120 manufactured by Rigaku Co., Ltd.
Temperature rise rate: 10 ° C / min Measurement temperature: 25 to 750 ° C
[Refractive index]
Equipment: JA Woolam Japan Co., Ltd. High-speed spectroscopic ellipsometer M-2000

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 [Kyoeisha Chemical Co., Ltd., light acrylate THF-A]
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [manufactured by Toagosei Co., Ltd., Aronix (registered trademark) M-403]
EDPHA: Ethylene oxide-modified dipentaerythritol hexaacrylate [manufactured by Shin Nakamura Chemical Industry Co., Ltd., A-DPH-12E]
I784: Bis (cyclopentadienyl) Bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) Titanium [manufactured by BASF Japan Ltd., IRGACURE (registered trademark) 784)]
NPG: N-Phenylglycine [manufactured by 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'-dipropylthia dicarbocyanine iodine [manufactured by Tokyo Chemical Industry Co., Ltd., DiSC ₃ (5)]
RB: Rose Bengal [manufactured by Tokyo Chemical Industry Co., Ltd.]
DMAc: N, N-dimethylacetamide THF: tetrahydrofuran

[Production Example 1] Production of a triazine ring-containing hyperbranched polymer (HB-TmDA)

Under a nitrogen atmosphere, 456 g of DMAc was charged in a 1 L four-necked flask and cooled to −10 ° C. by 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 prepared 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 added dropwise to the four-necked flask, and the mixture was stirred for 30 minutes after the completion of the addition. ..
This reaction solution was added dropwise to 622 g of DMAc in a 2 L four-necked flask separately heated to 85 ° C. by an oil bath over 1 hour using a liquid feed pump, and further stirred for 1 hour for polymerization. Then, 113.95 g (1.224 mol) of aniline was added, and the mixture was further stirred for 1 hour to complete the reaction.
It was cooled to room temperature (approximately 23 ° C.) by an ice bath. After adding 116.36 g (1.15 mol) of triethylamine to this, the mixture was further stirred for 30 minutes, and hydrochloric acid produced as a by-product of the polymerization reaction was quenched. The precipitated hydrochloride salt was filtered off. This filtrate was added to a mixed solution of 279.29 g of a 28 mass% aqueous ammonia solution and 8,820 g of ion-exchanged water to reprecipitate the 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 the target triazine ring-containing hyperbranched polymer fine particles [1a] (hereinafter abbreviated as HB-TmDA).
^{The 1} H NMR spectrum of the obtained HB-TmDA is shown in FIG. 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, and the polydispersity Mw / Mn (weight average molecular weight / number average molecular weight) is 3.4, _5%. It was 419 ° C. The density of HB-TmDA obtained from the film density measurement was 1.32 g / cm ³ .
The obtained 10% by mass cyclohexanone solution of HB-TmDA was spin-coated on a glass substrate (200 rpm × 5 seconds, then 2,000 rpm × 30 seconds), 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.

[Example 1]
<Preparation of composition for volume hologram recording material>
(A) As hydroxyalkyl (meth) acrylate, 4HBA 764 mg, (b) As a polymerizable compound, DPHA 303 mg, (c) As a triazine ring-containing hyperbranched polymer, HB-TmDA 320 mg obtained in Production Example 1, and (d). A composition for a volumetric hologram recording material was prepared by mixing 3.1 mg of I784 as a photopolymerization initiator and stirring at 50 ° C. for 72 hours.
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.

<Preparation of volume hologram recording medium>
A metal leaf 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 composition for volume hologram recording material is dropped on the center of the slide glass (region sandwiched between the spacers) to form a volume hologram recording layer. bottom. Then, another slide glass was put on the formed volume hologram recording layer so as to sandwich the formed volume hologram recording layer, and a volume hologram recording medium was produced.

<Measurement of each physical property value during volume hologram recording>
The obtained volume hologram recording medium was subjected to double luminous flux interference exposure by the apparatus shown in FIG. 2 to attempt to record the volume hologram. ^{A two-} luminous flux interference exposure (lattice spacing 1 μm) was performed on the _{volume hologram recording medium using an Nd: YVO 4} laser having a wavelength of 532 nm at an exposure power density of 250 mW / cm 2. Nd: YVO ₄ light emitted from the laser is split into two by the half mirror through the beam expander is irradiated onto the volume hologram recording medium via mirrors respectively, interference fringes of the two light to form a volume hologram is recorded ..
At the same time, the volume hologram recording medium is irradiated with a helium neon (He-Ne) laser having a wavelength of 632.8 nm, which is not exposed to the volume hologram recording medium, and the diffracted light is detected by an optical detector to monitor and diffract the hologram formation process. The efficiency was evaluated. In addition, the angle dependence of the diffraction efficiency after exposure was measured, and the film thickness of the sample after exposure was calculated. Further, 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 the film thickness. The results are also shown in Table 1. The change of Δn with respect to the exposure time is shown in FIG.

[Comparative Example 1]
The volume fraction of HB-TmDA was 19.9 in the same manner as in Example 1 except that 4HBA764 mg was changed to THFA (density 1.064 g / cm ³ ) 704 mg and NVP (density 1.043 g / cm ^{3) 60 mg.} A volume hologram medium having a volume percentage was prepared and evaluated in the same manner. The results are also shown in Table 1. The change of Δn with respect to the exposure time is shown in FIG.

[Comparative Example 2]
An attempt was made to prepare a composition for a volume hologram recording material by the same method as in Example 1 except that 4HBA 764 mg was changed to MMA 764 mg. However, since HB-TmDA was not dissolved and a uniform composition could not be obtained, subsequent formation of volume holograms and evaluation of diffraction efficiency could not be performed.

[Comparative Example 3]
An attempt was made to prepare a composition for a volume hologram recording material by the same method as in Example 1 except that 4HBA 764 mg was changed to BnMA 764 mg. However, since HB-TmDA was not dissolved and a uniform composition could not be obtained, subsequent formation of volume holograms and evaluation of diffraction efficiency could not be performed.

As shown in Table 1, the composition of the present invention (Example 1) has an extremely high saturated refractive index as compared with the composition to 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.}
Further, in the composition in which an unsubstituted alkyl (meth) acrylate is added instead of the hydroxyalkyl (meth) acrylate of the present invention (Comparative Example 2) and the composition in which aralkyl (meth) acrylate is added (Comparative Example 3). Obtained the result that the hyperbranched polymer did not dissolve and a uniform composition could not be obtained.

[Example 2]
(A) 4,HBA 3,918 mg as (meth) hydroxyalkyl acrylate, (b) EDPHA 159 mg as a polymerizable compound, (c) HB-TmDA 913 mg obtained in Production Example 1 as a triazine ring-containing hyperbranched polymer, and ( d) A composition for a volumetric hologram recording material was prepared by mixing 6.36 mg of NPG as a photopolymerization initiator and 3.18 mg of RB as a sensitizer and stirring at 50 ° C. for 24 hours.
Using the obtained composition, a volume hologram recording medium was prepared in the same manner as in Example 1 except that the spacer thickness was changed to 5 μm and the exposure power density was ^{changed to 5 mW / cm 2, and the refractive index was modulated.} The change in exposure time of the quantity (Δn) and the saturated refractive index modulation amount (Δn _sat ) were evaluated. The results are also shown in Table 2. The change of Δn with respect to the exposure time is shown in FIG.
Here, the density of 4HBA is 1.04 g / cm ³ , the density of EDPHA is 1.15 g / cm ³ , and the density of HB-TmDA is 1.32 g / cm ³ , and their 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. That is, it was 15.1% by volume.

[Examples 3 to 5]
A volume hologram medium having a volume fraction of HB-TmDA having a value shown in Table 2 was prepared by the same method as in Example 2, and evaluated in the same manner. The results are also shown in Table 2. Further, the change of Δn with respect to the exposure time is shown in FIG. 6 (Example 3), FIG. 7 (Example 4), and FIG. 8 (Example 5).

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 adopting hexaacrylate, (d) N-phenylglycine as a photopolymerization initiator, and rosebengal as a sensitizer, the composition of Example 1 ((b) dipentaerythritol pentaacrylate / di as a polymerizable compound). More than pentaerythritol hexaacrylate mixture and (c) bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium as photopolymerization initiator) It was confirmed that the saturated refractive index modulation amount Δn _{sat was higher.}

[Example 6]
(A) 4,HBA 3,632 mg as (meth) hydroxyalkyl acrylate, (b) EDPHA 157 mg as a polymerizable compound, (c) HB-TmDA 1,202 mg 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 volumetric hologram recording material.
Here, the density of 4HBA is 1.04 g / cm ³ , the density of EDPHA is 1.15 g / cm ³ , and the density of HB-TmDA is 1.32 g / cm ³ , and their volumes are 4HBA: 3.632, respectively. ÷ 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.

<Preparation of volume hologram recording medium>
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.

<Measurement of each physical property value during volume hologram recording>
The obtained volume hologram recording medium was subjected to double luminous flux interference exposure by the apparatus shown in FIG. 9, and recording of the volume hologram was attempted. A solid-state laser [05-01 Borero manufactured by Cobolt] having a wavelength of 640 nm was used to perform double luminous flux interference exposure (lattice spacing 0.5 μm) at ^{an exposure power density of 5 mW / cm 2 on the volume hologram recording medium.} The light emitted from the solid-state laser was divided into two by a half mirror via a beam expander, and each of them was irradiated to a volume hologram recording medium through the mirror, and 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. In addition, the angle dependence of the diffraction efficiency after exposure was measured, and the film thickness of the sample after exposure was calculated. Further, 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 the film thickness. The results are also shown in Table 3. The change of Δn with respect to the exposure time is shown in FIG.

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

1 Hologram recording medium 2a Nd: YVO ₄ laser 2b solid-state 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 Optical detector

Claims (9)

A composition for a volumetric hologram recording material used to form a pattern by pattern exposure.
(A) (Meta) hydroxyalkyl acrylate,
(B) A polymerizable compound different from the component (a),
A composition for a volume hologram recording material containing (c) a triazine ring-containing hyperbranched polymer and (d) a photopolymerization initiator. The first aspect of the present invention, wherein the ratio of the component (a), the component (b), and the component (c) to the total volume of the component (c) is 3% by volume or more and 50% by volume or less. Composition for volumetric hologram recording material. The composition for a volume hologram recording material according to claim 1 or 2, wherein the pattern exposure is interference exposure and is used for forming a hologram by the interference exposure. 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. A volume hologram recording layer containing the composition for a volume hologram recording material according to any one of claims 1 to 4. A volume hologram recording medium including 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 plane and is arranged between two transparent substrates facing the planes. A pattern including 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 pattern exposure to the coating film. Forming method. The pattern forming method according to claim 8, wherein the pattern exposure is interference exposure.

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