JP2010091827A - Method for manufacturing hologram recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a hologram recording material that contains fine particles of an organic group-containing composite metal compound containing silicon and a metal other than silicon, and a photopolymerizable compound, and has excellent uniformity and stability. <P>SOLUTION: The method for manufacturing a hologram recording material includes steps of: hydrolyzing and condensing an alkoxide compound of a metal other than Si to generate an oxide of the other metal; mixing the oxide of the other metal with an Si-containing material containing at least one compound selected from a group consisting of Si alkoxide compounds, silanol compounds and condensates of the compounds; advancing hydrolysis and condensation of the Si-containing material as well as condensing a residual active group present in the oxide of the other metal with a silyloxy group of the Si-containing material; and adding a photopolymerizable compound to the reaction system. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hologram recording material suitable for volume hologram recording, more specifically, a hologram recording material comprising organic group-containing composite metal compound fine particles containing silicon and a metal other than silicon, and a photopolymerizable compound. It relates to a method of manufacturing. In particular, the present invention relates to a method for producing a hologram recording material suitable for recording / reproduction with blue laser light as well as green laser light.

  Research and development of holographic memory is underway as a recording technology that enables high-capacity and high-speed transfer. Properties required for the hologram recording material include high refractive index change, high sensitivity, low scattering, environmental resistance, that is, storage stability, durability, low dimensional change, and high multiplicity during recording.

  As a hologram recording material, an organic-inorganic hybrid material mainly composed of an inorganic matrix and a photopolymerizable monomer has attracted attention and has been studied. The inorganic matrix is excellent in environmental resistance and durability.

  For example, Japanese Patent No. 2953200 discloses an optical recording film containing a photopolymerizable monomer or oligomer and a photopolymerization initiator in an inorganic substance network film. Monofunctional (meth) acrylic acid esters, polyfunctional (meth) acrylic acid esters, and the like are disclosed as photopolymerizable monomers (paragraph [0017]).

  Japanese Patent Application Laid-Open No. 11-344917 discloses an optical recording medium containing a photoactive monomer in an organic-inorganic hybrid matrix. As the photoactive monomer, an acrylate monomer such as diethylene glycol monoethyl ether acrylate is disclosed (paragraph [0018]).

  Japanese Patent Laid-Open No. 2002-236439 discloses an organic-inorganic obtained by copolymerizing an organometallic compound containing an ethylenically unsaturated double bond as a main chain component and an organic monomer having an ethylenically unsaturated double bond. A hologram recording material including a matrix composed of a hybrid polymer and / or a hydrolyzed polycondensate thereof, a photopolymerizable compound, and a photopolymerization initiator is disclosed. Examples of the photopolymerizable compound include a photoradical polymerizable compound and a photocationic polymerizable compound (paragraph [0041]), and a (meth) acrylic acid ester monomer is disclosed as the photoradical polymerizable compound (paragraph [ 0042] to [0043]).

JP-A-2005-77740 includes metal oxide particles, a polymerizable monomer, and a photopolymerization initiator,
The metal oxide particles are surface-treated with a surface treatment agent in which a hydrophobic group and a functional group capable of dehydration condensation with a hydroxyl group on the surface of the metal oxide particles are bonded to a metal atom,
A hologram recording material is disclosed in which the metal atom is selected from the group consisting of titanium, aluminum, zirconium, and chromium. As the polymerizable monomer, a (meth) acrylic acid ester monomer is disclosed (paragraph [0020]).

  Japanese Unexamined Patent Application Publication No. 2005-99612 discloses a hologram recording material containing a compound having one or more polymerizable functional groups, a photopolymerization initiator, and colloidal silica particles. As the polymerizable functional group, an acrylate monomer is disclosed (paragraphs [0019] to [0022]), and acrylamides (ethylenebisacrylamide) are disclosed as another example (paragraph [0023]).

  Japanese Patent Application Laid-Open No. 2005-321684 has at least two kinds of metals (Si, Ti), oxygen, and aromatic groups, and two aromatic groups are directly bonded to one metal (Si). A hologram recording material containing an organometallic compound having an organometallic unit and a photopolymerizable compound is disclosed. Examples of the photopolymerizable compound include a radical polymerizable compound and a cationic polymerizable compound (paragraph [0039]), and a (meth) acrylic acid ester is disclosed as the radical polymerizable compound (paragraph [0041]).

  Japanese Patent Application Laid-Open No. 2008-58834 discloses a hologram recording medium including at least a hologram recording material layer, and the hologram recording material layer includes an organometallic compound having a Ti—O bond and a Si—O bond, a photopolymerizable compound, and And a recording medium having a light transmittance of 50% or more at a wavelength of 405 nm or a light reflectance of 25% or more at a wavelength of 405 nm is disclosed. As the photopolymerizable compound, (meth) acrylic acid ester is disclosed (paragraph [0060]).

  Japanese Patent Laid-Open No. 2008-58838 includes Si and at least one selected from the group consisting of Ta and Zr as a metal, and a complex-forming ligand is coordinated to Ta and / or Zr. A hologram recording material containing a metal oxide and a photopolymerizable compound is disclosed. The complex-forming ligand is selected from the group consisting of β-dicarbonyl compounds, polyhydroxylated ligands, and α- or β-hydroxy acids. Examples of the photopolymerizable compound include a radical polymerizable compound and a cationic polymerizable compound (paragraph [0046]), and a (meth) acrylic acid ester is disclosed as the radical polymerizable compound (paragraph [0047]).

Japanese Patent No. 2953200 JP-A-11-344917 JP 2002-236439 A JP 2005-77740 A Japanese Patent Laid-Open No. 2005-99612 JP-A-2005-321684 JP 2008-58834 A JP 2008-58838 A

  In the said patent document, (meth) acrylic acid ester is disclosed as a photopolymerizable monomer. However, (meth) acrylic acid esters are easily hydrolyzed under acidic or basic conditions. In addition, (meth) acrylic acid esters are also susceptible to transesterification by interaction with metal alkoxide compounds or multimers thereof, which are metal oxide matrix forming materials in the sol-gel method. Therefore, when (meth) acrylic acid ester is applied as a photopolymerizable monomer to the metal oxide matrix, (meth) acrylic acid ester is gradually decomposed, resulting in deterioration of hologram recording characteristics.

  On the other hand, when a mixture of an alkoxide compound of Si and an alkoxide compound of a metal other than Si (Ti, Zr, Ta, Sn, Al, Zn) is subjected to a sol-gel reaction, an Si alkoxide compound is obtained. Is generally low in the rate of hydrolysis and polymerization reaction, and the alkoxide compound of other metals other than Si has a high rate of hydrolysis and polymerization reaction, so that the oxides of other metals other than Si aggregate and become homogeneous. No sol-gel reaction product is obtained.

  The shorter the wavelength of the recording / reproducing laser, the higher the mechanical strength, the high flexibility, the high homogeneity, and the environmental resistance (storage stability) of the hologram recording layer are required. Insufficient mechanical strength of the hologram recording layer leads to an increase in shrinkage during recording and a decrease in storage reliability. In particular, in order to obtain a sufficient contrast of refractive index modulation with a recording / reproducing laser in a short wavelength region, it is preferable to increase the microscopic mechanical strength to some extent and suppress monomer movement and dark reaction after recording exposure. If the hologram recording layer is not sufficiently flexible, the movement of the photopolymerizable monomer during recording will be hindered, leading to a decrease in sensitivity. If the homogeneity is insufficient, scattering will occur during recording / reproduction. / The reliability of the playback itself is reduced. The influence of scattering due to the inhomogeneity of the recording layer is more apparent in the recording / reproducing laser in the short wavelength region.

  An object of the present invention is to provide a method for producing a hologram recording material having excellent homogeneity and stability, comprising organic group-containing composite metal compound fine particles containing silicon and a metal other than silicon, and a photopolymerizable compound. There is to do. In particular, the object of the present invention is high refractive index change, flexibility, high sensitivity, low scattering, environmental resistance, durability, low dimensional change (holographic memory recording using a blue laser as well as a green laser). An object of the present invention is to provide a method for producing a hologram recording material suitable for volume hologram recording, in which low shrinkage) and high multiplicity are achieved.

  In order to suppress the decomposition of the photopolymerizable monomer, particularly (meth) acrylic acid ester, in the organic group-containing composite metal compound sol containing Si and another metal other than Si as a metal element, It has been found that it is important to eliminate reaction active sites present in oxides of metals other than Si.

The present invention includes the following inventions.
(1) A method for producing a hologram recording material comprising organic group-containing composite metal compound fine particles containing Si and another metal other than Si as a metal element, and a photopolymerizable compound,
Hydrolyzing and condensing a alkoxide compound of another metal other than Si to generate an oxide of the other metal;
Mixing the other metal oxide with a Si-containing material containing at least one selected from the group consisting of Si alkoxide compounds, silanol compounds, and condensates of these compounds;
A step of causing hydrolysis and condensation reaction of the Si-containing material to proceed, and a condensation reaction between a residual active group present in the oxide of the other metal and a silyloxy group of the Si-containing material;
Adding a photopolymerizable compound to the reaction system;
A method for producing a hologram recording material comprising:

  The residual active group present in the oxide of the other metal (M) is a residual hydroxyl group (M-OH), and a residual alkoxyl group (M-OR) that generates a hydroxyl group (M-OH) by hydrolysis. ) Is also included. Here, -OR represents an alkoxy group.

  (2) The method for producing a hologram recording material according to (1), wherein the metal other than Si is selected from the group consisting of Ti, Zr, Ta, Sn, Zn, and Al.

(3) Before hydrolysis of an alkoxide compound of a metal other than Si,
The method for producing a hologram recording material according to (1) or (2), further comprising a step of coordinating a ligand to an alkoxide compound of a metal other than Si.

  (4) The production of the hologram recording material according to the above (3), wherein the ligand is selected from the group consisting of a β-dicarbonyl compound, a polyhydroxylated ligand, and an α- or β-hydroxy acid. Method.

(5) further comprising hydrolyzing the Si alkoxide compound,
The method for producing a hologram recording material according to any one of (1) to (4), wherein the hydrolysis product is used as a Si-containing material.

(6) The Si alkoxide compound has the following general formula (I):
(R ₁₁ ) m Si (OR ₁₂ ) n (I)
(In the formula, R ₁₁ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₁₂ represents an alkyl group which may have a substituent. , M represents 1, 2 or 3, n represents 1, 2 or 3, provided that m + n is 4. R ₁₁ may be different depending on m, and R ₁₂ may be different depending on n. .)
The method for producing a hologram recording material according to any one of (1) to (5), represented by:

(7) The alkoxide compound of Si in the general formula (I),
R ₁₁ represents an aryl group which may have a substituent, R ₁₂ represents an alkyl group which may have a substituent, m represents 2, and n represents 2. (6) The method for producing a hologram recording material according to (6).

(8) The silanol compound has the following general formula (II):
(R ₂₁ ) j Si (OH) k (II)
(In the formula, R ₂₁ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, j represents 1, 2 or 3, provided that j + k is 4. R ₂₁ may be different depending on j.)
The method for producing a hologram recording material according to any one of (1) to (4), which is represented by:

(9) The silanol compound in the general formula (II),
The method for producing a hologram recording material according to the above (8), wherein R ₂₁ represents an aryl group which may have a substituent, j represents 2, and k represents 2.

  (10) The method for producing a hologram recording material according to any one of (1) to (9), wherein the photopolymerizable compound is selected from (meth) acrylic acid esters.

  (11) The method for producing a hologram recording material according to any one of (1) to (10), further comprising a step of adding a photopolymerization initiator to the reaction system.

  (12) A hologram recording material obtained by the production method according to any one of (1) to (11) above.

  (13) A hologram recording medium having a hologram recording layer made of a hologram recording material obtained by the production method according to any one of (1) to (11) above.

  (14) The hologram recording medium according to (13), which is recorded / reproduced by laser light having a wavelength of 350 to 450 nm.

  (15) The hologram recording medium according to (13) or (14), wherein the hologram recording layer has a thickness of at least 100 μm.

  In the present invention, first, an alkoxide compound of a metal other than Si, which has a higher rate of hydrolysis and condensation reaction than the alkoxide compound of Si, is hydrolyzed and condensed to produce an oxide of the other metal. Next, the other metal oxide is mixed with a Si-containing material containing at least one selected from the group consisting of Si alkoxide compounds, silanol compounds, and condensates of these compounds. Subsequently, the hydrolysis and condensation reaction of the Si-containing material is allowed to proceed, and the residual active group present in the oxide of the other metal is subjected to a condensation reaction with the silyloxy group of the Si-containing material.

  By carrying out these steps, reaction active sites derived from the other metal (M) raw material metal alkoxide compound, for example, an alkoxyl group (M-OR) of a metal alkoxide compound or a condensate thereof, or a hydrolyzed hydroxyl group (M-OH) is subjected to a condensation reaction with the silyloxy group of the Si-containing material and disappears. Since the reaction active site of the other metal (M) disappears, decomposition of the photopolymerizable monomer, particularly (meth) acrylic acid ester added in the subsequent step is suppressed. And since the hydrolysis and condensation reaction of the alkoxide compound of the metal (M) other than Si is performed before the mixing of the Si-containing material, the oxide of the metal (M) other than Si aggregates. And a homogeneous sol-gel reaction product is obtained.

  Thus, according to the present invention, the photopolymerizable compound and the organic group-containing composite metal compound fine particle containing Si and other metal other than Si functioning as a matrix or a dispersion medium of the photopolymerizable compound are included. Thus, a hologram recording material excellent in homogeneity and stability is produced. The obtained hologram recording material is suitable for recording / reproducing with blue laser light as well as green laser light.

  The hologram recording material in the present invention contains organic group-containing composite metal compound fine particles containing Si and another metal (M) other than Si as metal elements, and a photopolymerizable compound (organic monomer).

  The metal other than Si is not particularly limited, but may be selected from the group consisting of Ti, Zr, Ta, Sn, Zn, and Al. By including two or more kinds of metals as constituent elements, it is easy to control characteristics such as refractive index, which is preferable in recording material design.

  In the production method of the present invention, first, a step of hydrolyzing and condensing an alkoxide compound of a metal other than Si to generate an oxide of the other metal is performed.

The metal alkoxide compound other than Si is not particularly limited. For example, tetra n-propoxy titanium [Ti (O-nPr) ₄ ], tetraisopropoxy titanium [Ti (O-iPr) ₄ ]. , Alkoxide compounds of titanium such as tetra n-butoxy titanium [Ti (O-nBu) ₄ ]; pentaethoxy tantalum [Ta (OEt) ₅ ], tetraethoxy tantalum pentane dionate [Ta (OEt) ₄ (C ₅ H ₇ Tantalum alkoxide compounds such as O ₂ )]; zirconium alkoxide compounds such as tetra-t-butoxyzirconium [Zr (O-tBu) ₄ ], tetra-n-butoxyzirconium [Zr (O-nBu) ₄ ]; tetra-t- butoxy tin _{[Sn (O-tBu) 4} ], tetra n- butoxy tin _{[Sn (O-nBu) 4} ] Alkoxide compound of tin; diethoxy zinc [Zn (OEt) _2], dimethoxyethoxy zinc _{[Zn (OC 2 H 4 -OCH} 3) 2] alkoxide compound of zinc and the like; tri i- propoxy aluminum [Al (O-iPr ₃ ], tri-t-butoxyaluminum [Al (O-tBu) ₃ ], tri-s-butoxyaluminum [Al (O-sBu) ₃ ], tri-n-butoxyaluminum [Al (O-nBu) ₃ ], etc. Examples thereof include aluminum alkoxide compounds. In addition to these, a metal alkoxide compound can be used.

  Further, a multimer of metal alkoxide compounds (corresponding to a partial hydrolysis-condensation product of metal alkoxide compounds) may be used. For example, a titanium butoxide multimer (corresponding to a partial hydrolysis-condensation product of tetrabutoxy titanium) may be used.

  The hydrolysis and polycondensation reaction can be carried out under the same operations and conditions as in the known sol-gel method. For example, an alkoxide compound of a metal other than Si is dissolved in an appropriate good solvent to form a homogeneous solution, and an appropriate acid catalyst is dropped into the solution, and the solution is stirred in the presence of water to react. It can be carried out. The amount of water added is preferably 1 to 10 times the molar amount of the metal alkoxide compound as a starting material. When the amount of water added is less than 1 mole relative to the metal alkoxide compound, the polymerization reaction does not proceed sufficiently, and many alkoxyl groups remain. On the other hand, even if the amount of water added is more than 10-fold mol with respect to the metal alkoxide compound, there is no significant effect in reducing the residual amount of alkoxyl groups, and 10-fold mol or less is sufficient.

  Examples of such a solvent include water; alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; ethers such as diethyl ether, dioxane, dimethoxyethane, and tetrahydrofuran; N-methylpyrrolidone, acetonitrile, N, N— Examples include dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetone, and benzene. What is necessary is just to select suitably from these. Or it can also be set as these mixed solvents. The amount of the solvent is not limited, but may be 10 to 1000 parts by weight with respect to 100 parts by weight of the entire metal alkoxide compound (alkoxide compound of other metal than Si + alkoxide compound of Si).

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, and the like. Organic acids and the like.

  Although it depends on the reactivity of the metal alkoxide compound, the hydrolysis polymerization reaction can generally be performed at room temperature (25 ° C.), and is a temperature up to the boiling point of the solvent used, for example, a temperature of about 0 to 150 ° C., preferably It can be performed at a temperature of room temperature to about 50 ° C. The reaction time may be appropriately determined in relation to the reaction temperature, but is about 0.1 to 240 hours. The reaction may be performed under an inert atmosphere such as nitrogen gas, or may be performed under reduced pressure of about 0.5 to 1 atm while removing alcohol generated by the polymerization reaction.

  In the present invention, it is preferable to perform a step of coordinating an organic polydentate ligand to an alkoxide compound of a metal other than Si before hydrolysis of the alkoxide compound of a metal other than Si. As the organic ligand, a polydentate ligand is preferable.

  The polydentate ligand is a so-called chelate ligand, and examples thereof include β-dicarbonyl compounds, polyhydroxylated ligands, α- or β-hydroxy acids, ethanolamines, and the like. Examples of the β-dicarbonyl compound include β-diketones such as acetylacetone (AcAc) and benzoylacetone, and β-ketoesters such as ethyl acetoacetate (EtAcAc). Polyhydroxylated ligands include glycols (especially those of the 1,3-diol type, such as 1,3-propanediol, 2-ethyl-1,3-hexanediol), α- or β-hydroxy acids Examples thereof include lactic acid, glyceric acid, tartaric acid, citric acid, tropic acid, and benzylic acid. Examples of other ligands include oxalic acid.

  Aromatic carboxylic acids are also preferred as the ligand. An aromatic carboxylic acid is a compound in which one or more carboxylic acids (—COOH) are bonded directly to the aromatic ring (Ar). Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, o-, m-, or p-toluic acid, o-, m-, or p-methoxybenzoic acid; aromatics such as phthalic acid and terephthalic acid Group dicarboxylic acids.

  When an alkoxide compound of a metal other than Si (Ti, Zr, Ta, Sn, Al, Zn, etc.) is subjected to a sol-gel reaction, the rate of hydrolysis and polymerization reaction is generally large. The generated metal oxide may aggregate. By coordinating the organic ligand, the rate of hydrolysis and polymerization reaction can be suppressed, so that a more homogeneous sol-gel reaction product can be obtained.

  Further, when an organic ligand is coordinated to an alkoxide compound of a metal other than Si, an organic group is introduced into the resulting composite metal compound fine particles. By introducing into the organic group, the compatibility between the composite metal compound fine particles functioning as a matrix or a dispersion medium and the photopolymerizable compound is further improved.

  For example, in the case of a Ti alkoxide compound, 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl- It is preferable to coordinate a glycol such as 2,4-pentanediol.

  The above-mentioned glycol (ie, 1,3-diol) is easy to be multidentately coordinated to the Ti atom of the Ti alkoxide compound raw material, satisfies the coordinated position of the Ti atom, and is still another coordination compound during the sol-gel reaction. Is considered to inhibit hydrolysis and polymerization reaction. When the glycol is coordinated to the Ti alkoxide compound, the Ti alkoxide compound such as tetrabutoxy titanium and tetraethoxy titanium and the glycol are mixed in a solvent such as ethanol and butanol at room temperature, for example, and stirred. Good. In this case, the same solvent as that used in the sol-gel reaction may be used as the solvent. In this way, an alkoxide compound of Ti coordinated with glycol is prepared.

  In the case of a Ti alkoxide compound, it is also preferable to coordinate polyalkylene glycol as glycol. Examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

  Like the 1,3-diol, the polyalkylene glycol described above easily coordinates to the Ti atom of the Ti alkoxide compound raw material, satisfies the coordination position of the Ti atom, and has another coordination property during the sol-gel reaction. Inhibits the compound from coordinating to the Ti atom. Coordination of the polyalkylene glycol to the Ti alkoxide compound is preferably performed in the same manner as in the case of 1,3-diol coordination. Among the above-described polyalkylene glycols, dipropylene glycol is preferable from the viewpoint of coordination ability and availability.

For example, a polydentate ligand is coordinated to an alkoxide compound Zr (OR) ₄ (wherein R is an alkyl group) of Zr, and the alkoxide compound such as Zr (OR) ₂ (AcAc) ₂ is changed. As a result, the number of alkoxyl groups that can contribute to hydrolysis and polymerization reaction is reduced, and further, the reactivity of the alkoxyl group is suppressed by the steric factor of the chelate ligand such as acetylacetone (AcAc), It is considered that hydrolysis and polymerization reaction are suppressed by the above. The same applies to the alkoxide compound Ta (OR) ₅ of Ta.

Further, for example, an aromatic carboxylic acid is coordinated to an alkoxide compound Zr (OR) ₄ (wherein R is an alkyl group) of Zr, and a cluster containing several Zr, Zr (OR) ₃ (HOOCAr), Zr It is thought that it changes to Zr alkoxide compounds such as (OR) ₂ (HOOCAr) ₂ and Zr (OR) (HOOCAr) ₃ . Or it is thought that aromatic carboxylic acid may coordinate over Zr of two molecules of Zr alkoxide. As a result, the number of alkoxyl groups that can contribute to the hydrolysis and polymerization reaction is reduced, and further, the reactivity of the alkoxyl group is suppressed by the steric factor of the aromatic carboxylic acid compound, thereby causing hydrolysis and polymerization reaction. Is considered to be suppressed.

  The amount of the organic ligand to be used is not particularly limited, but may be appropriately determined based on the amount of the alkoxide compound of the metal (M) other than the Si in consideration of the reaction activity suppressing action. For example, the molar ratio (organic ligand / M) of the organic ligand to the metal atom (M) of the alkoxide compound of the metal (M) other than Si is 0.8 / 1 or more and 3/1 or less, It is preferable to set it to 1/1 or more and 2.5 / 1 or less, more preferably 1.5 / 1 or more and 2/1 or less.

  Thus, by performing the step of coordinating the polydentate ligand to the alkoxide compound of the other metal other than Si before the hydrolysis of the alkoxide compound of the other metal other than Si, An oxide sol of the other metal having a uniform shape can be generated.

  Next, a step of mixing the generated oxide of the other metal and the Si-containing material is performed. As the Si-containing material, a material containing at least one selected from the group consisting of Si alkoxide compounds, silanol compounds, and condensates of these compounds is used.

A variety of Si alkoxide compounds can be used. The alkoxide compound of Si is, for example, the general formula (I):
(R ₁₁ ) m Si (OR ₁₂ ) n (I)
It is good to use what is represented by.

Here, R ₁₁ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, R ₁₂ represents an alkyl group which may have a substituent, m represents 1, 2 or 3, n represents 1, 2 or 3, provided that m + n is 4. R ₁₁ may be different depending on m, and R ₁₂ may be different depending on n. Included in this formula (I) is an organosilicon compound having a carbon-silicon direct bond.

The alkyl group represented by R ₁₁ and R ₁₂ is usually a lower alkyl group having about 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and the like. It is done. Examples of the aryl group R ₁₁ represents a phenyl group. The alkyl group and aryl group may have a substituent. Examples of the substituent include a fluorine atom.

As the alkoxide compound of Si, in the general formula (I), R ₁₁ represents an aryl group which may have a substituent, R ₁₂ represents an alkyl group which may have a substituent, A silicon diaryl dialkoxide compound in which m represents 2 and n represents 2 is preferred.

Specific examples include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltri Ethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane (above, m = 1, n = 3);
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane (m = 2, n = 2) and the like. By selecting these silicon alkoxide compounds, the hardness and flexibility of the matrix after gelation can be adjusted. Diphenyldimethoxysilane and diphenyldiethoxysilane are preferred because they can impart flexibility to the matrix after gelation and the compatibility with the photopolymerizable compound is improved.

  When a monoalkoxysilane (m = 3, n = 1) such as trimethylmethoxysilane is present, the polymerization reaction is stopped, so that the monoalkoxysilane can be used to adjust the molecular weight. Moreover, although other than the said general formula (I), you may use together tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. suitably.

  The Si-containing material may be mixed with the other metal oxide that has produced the Si alkoxide compound, but the Si alkoxide compound is hydrolyzed to some extent, and the hydrolyzate is mixed with the other metal oxide. You may mix.

  A silanol compound may be used as the Si-containing material. The silanol compound is a compound having a silanol group Si—OH, and is equivalent to a compound obtained by hydrolyzing the alkoxyl group of the Si alkoxide compound.

Examples of the silanol compound include the following general formula (II):
(R ₂₁ ) j Si (OH) k (II)
It is good to use what is represented by.

Here, R ₂₁ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, j represents 1, 2 or 3, provided that j + k is 4. . R ₂₁ may be different depending on j. What is included in this formula (II) is an organosilicon compound having a carbon-silicon direct bond.

The alkyl group represented by R ₂₁ is usually a lower alkyl group having about 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. Examples of the aryl group R ₂₁ represents a phenyl group. The alkyl group and aryl group may have a substituent. Examples of the substituent include a fluorine atom.

The silanol compound is preferably a disilanol compound in which R ₂₁ represents an aryl group which may have a substituent in the general formula (II), j represents 2, and k represents 2. Specific examples of the disilanol compound include diphenyldisilanol, phenylmethyldisilanol, and phenylethyldisilanol.

  When monosilanol (j = 3) such as trimethylsilanol is present, the polymerization reaction is stopped, so that monosilanol can be used for adjusting the molecular weight.

  A Si alkoxide compound and / or a condensate of a silanol compound may be used as the Si-containing material.

  The mixing of the other metal oxide and the Si-containing material is generally performed at room temperature, and may be performed at the same temperature as the hydrolysis polymerization reaction of the alkoxide of the other metal.

The usage amount of the other metal oxide and the Si-containing material may be appropriately determined so that the composite metal compound fine particles have a desired refractive index in the design of the recording material. For example, the number of Si in the composite metal compound fine particles (s), the number of other metals (Ti, Zr, Ta, Sn, Al, Zn) other than Si (m) is:
0.3s ≦ m ≦ 3s
It is preferable that the relationship is satisfied.

  Subsequently, the hydrolysis and condensation reaction of the Si-containing material is advanced, and the remaining active group present in the oxide of the other metal and the silyloxy group of the Si-containing material are subjected to a condensation reaction.

  Before mixing the Si-containing material, the other metal (M) oxide includes an alkoxyl group (M-OR) of a metal alkoxide compound or a condensate thereof, or a hydrolyzed hydroxyl group (M-OH). Such an active group remains. When the hydrolysis and condensation reaction of the Si-containing material proceeds after mixing the Si-containing material, at the same time, the remaining active group present in the oxide of the other metal (M) and the silyloxy group of the Si-containing material (Si—O—) condenses. In this way, reaction reactive sites present in the oxide of the other metal (M) disappear.

  The hydrolysis polymerization reaction at this time can be carried out under the same operation and conditions as the hydrolysis polymerization reaction of an alkoxide compound of a metal other than Si described above.

  As described above, an organic group-containing composite metal compound fine particle sol containing Si and a metal other than Si as a metal element is obtained. In the obtained composite metal compound in the form of fine particles, in addition to the bond (Si—OM) between Si atoms and other metal (M) atoms other than Si (Si—OM), oxygen atoms between Si atoms It is considered that a bond via Si (O—Si) and a bond via an oxygen atom between other metal (M) atoms other than Si (M—O—M) are included. The obtained sol is mainly composed of bonds between Si atoms via oxygen atoms (Si—O—Si) and does not contain metal (M) atoms other than Si, or other than Si. It is considered that fine particles containing mainly Si (M-O-M) bonds between metal (M) atoms and containing no Si atoms are also included.

  Next, the process of adding the photopolymerizable organic compound (organic monomer) mentioned later to the obtained sol-gel reaction system is performed. In order to mix uniformly, it is preferable to add and mix the photopolymerizable organic compound while the sol-gel reaction system containing the composite metal compound fine particles is in a sol state. Moreover, mixing of a photoinitiator and a photosensitizer can also be performed in this case.

  The photopolymerizable compound is a photopolymerizable organic monomer. As the photopolymerizable compound, a compound selected from a radical polymerizable compound and a cationic polymerizable compound can be used.

  The radically polymerizable compound is not particularly limited as long as it has one or more radically polymerizable unsaturated double bonds in the molecule. For example, a monofunctional or polyfunctional compound having a (meth) acryloyl group or a vinyl group can be used. Functional compounds can be used. The (meth) acryloyl group is a generic term for a methacryloyl group and an acryloyl group.

Among such radically polymerizable compounds, compounds having a (meth) acryloyl group include phenoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl (meth). Acrylate, cyclohexyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, etc. Monofunctional (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Polyfunctional (meth) acrylates such as polyethylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, 2,2-bis [4- (acryloxy-diethoxy) phenyl] propane;
However, it is not necessarily limited to these.

  In addition, as the compound having a vinyl group, monofunctional vinyl compounds such as monovinylbenzene (styrene) and ethylene glycol monovinyl ether; polyfunctional vinyl compounds such as divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether However, it is not necessarily limited to these.

  Only 1 type of radically polymerizable compound may be used, and 2 or more types may be used together. In the present invention, when the composite metal compound fine particles have a high refractive index and the organic polymer has a low refractive index, a low refractive index having no aromatic group among the above radical polymerizable compounds (for example, Those having a refractive index of 1.5 or less are preferred. In order to further improve the compatibility of the composite metal compound fine particles, more hydrophilic glycol derivatives such as polyethylene glycol (meth) acrylate and polyethylene glycol di (meth) acrylate are preferred.

  The structure of the cationically polymerizable compound is not particularly limited as long as it has at least one reactive group selected from a cyclic ether group and a vinyl ether group.

  Among such cationically polymerizable compounds, examples of the compound having a cyclic ether group include compounds having an epoxy group, an alicyclic epoxy group, or an oxetanyl group.

  Specific examples of compounds having an epoxy group include monofunctional epoxy compounds such as 1,2-epoxyhexadecane and 2-ethylhexyl diglycol glycidyl ether; bisphenol A diglycidyl ether, novolac-type epoxy resins, trisphenol methane triglycidyl Polyfunctional epoxy such as ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Compounds.

  Specific examples of the compound having an alicyclic epoxy group include 1,2-epoxy-4-vinylcyclohexane, D-2,2,6-trimethyl-2,3-epoxybicyclo [3,1,1]. Monofunctional compounds such as heptane, 3,4-epoxycyclohexylmethyl (meth) acrylate; 2,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., fat And polyfunctional compounds such as cyclic epoxy resins).

  Specific examples of the compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloctacene, 3-ethyl-3- (2-ethylhexyloxymethyl) octacene, and 3-ethyl-3- (cyclohexyloxymethyl). Monofunctional oxetanyl compounds such as oxacene; 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis ( 3-ethyl-3-oxetanylmethyl) And polyfunctional oxetanyl compounds such as ether and ethylene oxide-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether.

  Among the cationic polymerizable compounds, specific examples of compounds having a vinyl ether group include monofunctional compounds such as triethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether, 4-hydroxycyclohexyl vinyl ether; triethylene glycol divinyl ether, tetraethylene Polyfunctional compounds such as glycol divinyl ether, trimethylolpropane trivinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether, polyester divinyl ether, polyurethane polyvinyl ether and the like can be mentioned.

  Only 1 type of a cationically polymerizable compound may be used, and 2 or more types may be used together. Moreover, you may use the oligomer of the cationic polymerization compound of the said illustration as a photopolymerizable compound. In the present invention, when the composite metal compound fine particles have a high refractive index and the organic polymer has a low refractive index, a low refractive index having no aromatic group among the above cationic polymerizable compounds (for example, Those having a refractive index of 1.5 or less are preferred. In order to further improve the compatibility with the composite metal compound fine particles, a more hydrophilic glycol derivative such as polyethylene glycol diglycidyl ether is preferable.

  In the present invention, the photopolymerizable compound is used in an amount of, for example, about 5 to 1000% by weight, preferably 10 to 300% by weight, based on the total weight of the composite metal compound fine particles. If it is less than 5% by weight, it is difficult to obtain a large refractive index change during recording, and if it exceeds 1000% by weight, it is difficult to obtain a large refractive index change during recording.

  In the present invention, the hologram recording material preferably further contains a photopolymerization initiator corresponding to the wavelength of the recording light. When a photopolymerization initiator is contained, the polymerization of the photopolymerizable compound is promoted by exposure during recording, and higher sensitivity can be obtained.

  When a radical polymerizable compound is used as the photopolymerizable compound, a photo radical initiator is used. On the other hand, when a cation polymerizable compound is used as the photopolymerizable compound, a photo cation initiator is used.

  Examples of the photo radical initiator include Darocur 1173, Irgacure 784, Irgacure 651, Irgacure 184, and Irgacure 907 (all manufactured by Ciba Specialty Chemicals). The content of the photo radical initiator is, for example, about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, based on the radical polymerizable compound.

  As a photocation initiator, for example, an onium salt such as a diazonium salt, a sulfonium salt, or an iodonium salt can be used, and an aromatic onium salt is particularly preferable. In addition, iron-arene complexes such as ferrocene derivatives, arylsilanol-aluminum complexes, and the like can be preferably used, and may be appropriately selected from these. Specifically, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990 (all manufactured by Dow Chemical, USA), Irgacure 264, Irgacure 250 (all manufactured by Ciba Specialty Chemicals), CIT-1682 (Nippon Soda) Manufactured) and the like. The content of the photocation initiator is, for example, about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, based on the cationic polymerizable compound.

  It is preferable that a dye functioning as a photosensitizer corresponding to the recording light wavelength is contained in addition to the photopolymerization initiator. Examples of the photosensitizer include thioxanthones such as thioxanthen-9-one and 2,4-diethyl-9H-thioxanthen-9-one, xanthenes, cyanines, merocyanines, thiazines, acridines, Anthraquinones, squaryliums, etc. are mentioned. The amount of the photosensitizer used is preferably about 3 to 50% by weight of the photo radical initiator, for example, about 10% by weight.

  In this way, a hologram recording material liquid is obtained in which a photopolymerizable compound is uniformly mixed in a sol-state composite metal compound fine particle matrix. A film-like hologram recording material layer is obtained by applying a hologram recording material liquid on a substrate and further allowing solvent drying and sol-gel reaction to proceed. In this way, a hologram recording material layer in which the photopolymerizable compound is uniformly contained in the composite metal compound fine particle matrix is produced.

  In the obtained composite metal compound fine particle matrix, reaction active sites (M-OR or M-OH) of oxides of metals (M) other than Si have disappeared, so that the photopolymerizable organic compound Is suppressed from being adversely affected by the reaction active sites. Therefore, the temporal stability of the photopolymerizable compound is improved. In particular, when a (meth) acrylic acid ester that is easily affected by the reaction active site is used as the photopolymerizable compound, the advantages of the present invention are great.

  In addition, in the obtained composite metal compound fine particle matrix, it is considered that there are reaction active sites (Si-OR or Si-OH) of the oxide of Si. It is considerably smaller than the reaction active site (M-OR or M-OH) of oxides of other metals (M) other than Si. In particular, when preferable diphenyldimethoxysilane, diphenyldiethoxysilane or the like is used as the Si alkoxide compound, since two phenyl groups are directly bonded to Si, silanol groups (Si-OH) Activity is low.

  The hologram recording medium of the present invention comprises at least the hologram recording material layer. Usually, the hologram recording medium includes a support base (that is, a substrate) and a hologram recording material layer. However, the hologram recording medium may include only a hologram recording material layer without the support base. For example, by forming a hologram recording material layer on a substrate by coating and then peeling the hologram recording material layer from the substrate, a medium composed only of the hologram recording material layer can be obtained. In this case, the hologram recording material layer is a thick film of the order of mm, for example.

  The hologram recording medium of the present invention is based on the amount (initial) of the photopolymerizable compound present in the hologram recording layer before storage when the produced hologram recording medium is stored at 80 ° C. in a dry environment for 7 days. The residual amount of the photopolymerizable compound present in the hologram recording layer after storage is, for example, 50% or more, preferably 70% or more, and more preferably 85%. Under the above accelerated test conditions, the recording medium in which the residual amount of the photopolymerizable compound present in the hologram recording layer after storage is 50% or more has no problem in storage stability under a normal environment and is practical. Has recording characteristics.

The remaining amount (%) of the photopolymerizable compound in the hologram recording layer after storage can be determined, for example, as follows.
Part of the hologram recording layer of the hologram recording medium after preparation is scraped off, and infrared spectroscopic measurement is performed on the scraped sample to obtain characteristic absorption (for example, phenyl of Si-phenyl group) as a reference of the composite metal compound fine particle matrix. and strength Aph the characteristic absorption 1591~1592cm ^-1) group, the ratio of the intensity AC = O of characteristic absorption of the photopolymerizable compound (here the acrylate C = O bond characteristic absorption 1726~1727cm ^-1) (AC = O / Aph).
The hologram recording medium after preparation is stored at 80 ° C. in a dry environment for 7 days, a part of the hologram recording layer after storage is scraped, and the scraped sample is subjected to infrared spectroscopic measurement. Of the characteristic absorption (characteristic absorption 1591-1592 cm ⁻¹ of the phenyl group of the Si-phenyl group) and the characteristic absorption of the photopolymerizable compound (characteristic absorption 1726 to 1727 cm ^{−1 of the} C═O bond of the acrylate) ) Intensity BC = O (BC = O / Bph).

Since the amount of the phenyl group of the Si-phenyl group serving as a reference of the composite metal compound fine particle matrix before storage (initial) and after storage is unchanged,
Residual amount of photopolymerizable compound after storage (%)
= [(BC = O / Bph) / (AC = O / Aph)] × 100.

  You may pay attention to the characteristic absorption used as the appropriate reference | standard of the said composite metal compound fine particle matrix besides the phenyl group of Si-phenyl group. Moreover, you may pay attention to the suitable characteristic absorption of the said photopolymerizable compound besides the C = O coupling | bonding of an acrylate. The residual amount (%) of the photopolymerizable compound after storage can be determined by the same method as described above. In addition, a quantitative method other than infrared spectroscopic measurement may be used.

  The hologram recording medium of the present invention is suitable not only for green laser light but also for recording / reproducing with blue laser light having a wavelength of 350 to 450 nm. When reproducing with transmitted light, it is preferable to have a light transmittance of 50% or more at a wavelength of 405 nm, and when reproducing with reflected light, it is preferable to have a light reflectance of 25% or more at a wavelength of 405 nm.

  The hologram recording medium is a medium configured to reproduce with transmitted light (hereinafter referred to as a transmitted light reproduction type) or a medium configured to reproduce with reflected light (hereinafter referred to as a reflected light reproduction type) depending on the optical system apparatus used. Either.

  By using the hologram recording material layer, a hologram recording medium having a recording layer thickness of 100 μm or more suitable for data storage can be obtained. The hologram recording medium can be produced by forming a film-like hologram recording material on a substrate or sandwiching a film-like hologram recording material between substrates.

  When the hologram recording layer is irradiated with coherent light, the photopolymerizable organic compound (monomer) undergoes a polymerization reaction in the exposed area to become a polymer, and the photopolymerizable organic compound diffuses from the unexposed area to the exposed area. In addition, the exposed portion is further polymerized. As a result, a polymer-rich region and a polymer-poor region generated from the photopolymerizable organic compound are formed according to the light intensity distribution. At this time, the composite metal compound fine particles move from the polymer-rich region to the polymer-poor region, the polymer-rich region becomes the fine particle-poor region, and the polymer-poor region is the fine particle-rich region. Become. In this way, a region with a large amount of the polymer and a region with a large amount of the composite metal compound fine particles are formed by exposure, and when there is a difference in refractive index between the polymer and the fine particles, the refractive index depends on the light intensity distribution. Changes are recorded.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

[Example 1]
(Synthesis of matrix material)
Tetraisopropoxytitanium (Ti (O-iPr) ₄ , manufactured by Azmax) 5.82 g and 2-methylpentane-2,4-diol (manufactured by Tokyo Chemical Industry) 4.83 g were mixed with 1-methoxy-2-propanol 10. Mix in 5 mL at room temperature and stir for 5 minutes to obtain a solution. Ti (O-iPr) ₄ / the diol = 1/2 (molar ratio).

  To this solution, a solution consisting of 0.37 mL of water and 2.0 mL of the solvent 1-methoxy-2-propanol was added dropwise at room temperature while stirring, and stirring was continued for 1 hour to perform hydrolysis and condensation reaction, and to contain titanium. A reaction solution was obtained.

On the other hand, from 5.0 g of diphenyldimethoxysilane (Ph ₂ Si (OMe) ₂ , manufactured by Shin-Etsu Chemical Co., Ltd.) to 0.37 mL of water, 0.15 mL of 2N aqueous hydrochloric acid, and 5.0 mL of solvent 1-methoxy-2-propanol The resulting solution was added dropwise at room temperature while stirring, and stirring was continued for 1 hour to conduct a hydrolysis reaction to obtain a silicon-containing reaction solution.

  The obtained silicon-containing reaction solution was added to the titanium-containing reaction solution with stirring at room temperature, and then stirred at 80 ° C. for 1 hour to further perform hydrolysis and condensation reactions. Ti / Si = 1/1 (molar ratio). In this way, a sol solution was obtained.

(Photopolymerizable compound)
100 parts by weight of polyethylene glycol monoacrylate (manufactured by Kyoeisha Chemical Co., 130A) as a photopolymerizable compound, 3 parts by weight of Irgacure IRG-907 (Ciba Specialty Chemicals) as a photopolymerization initiator, and 2,4 as a photosensitizer -0.3 part by weight of diethyl-9H-thioxanthen-9-one was added to obtain a mixture containing a photopolymerizable compound.

(Hologram recording material)
The sol solution and the photopolymerizable compound mixture are mixed at room temperature and shielded from light so that the ratio of the matrix material (as a non-volatile component) is 85 parts by weight and the ratio of the photopolymerizable compound is 15 parts by weight. Then, the sol-gel reaction was sufficiently advanced for 1 hour to obtain a hologram recording material solution.

(Hologram recording medium)
The obtained hologram recording material solution was applied onto a glass substrate as described below and dried to obtain a recording medium sample.

A description will be given with reference to FIG. 1 showing a schematic section of a hologram recording medium.
A 1 mm thick glass substrate (22) provided with an antireflection film (22a) on one side was prepared. A spacer (24) having a predetermined thickness is placed on the surface of the glass substrate (22) where the antireflection film (22a) is not provided, the resulting hologram recording material solution is applied, dried at room temperature for 1 hour, and then It dried at 40 degreeC for 24 hours and volatilized the solvent. By this drying step, gelation (condensation reaction) of the composite metal compound fine particles was advanced to obtain a hologram recording material layer (21) having a dry film thickness of 150 μm in which the composite metal compound fine particles and the photopolymerizable compound were uniformly dispersed. .

  The hologram recording material layer (21) formed on the glass substrate (22) was covered with another 1 mm thick glass substrate (23) provided with an antireflection film (23a) on one side. At this time, the surface of the glass substrate (23) where the antireflection film (23a) was not provided was covered so as to be in contact with the surface of the hologram recording material layer (21). Thus, a hologram recording medium (11) having a structure in which the hologram recording material layer (21) was sandwiched between two glass substrates (22) and (23) was obtained.

A portion of the hologram recording layer of the hologram recording medium sample after preparation is scraped, and the scraped sample is subjected to infrared spectroscopic measurement (apparatus: Nicolet, Magna 760), which serves as a reference for the composite metal compound fine particle matrix. - I was determined and strength Aph characteristic absorption 1591～1592Cm ^-1 phenyl groups of the phenyl group, the ratio of the intensity AC = O of polyethylene glycol monoacrylate of C = O bond characteristic absorption 1726~1727cm ^-1. AC = O / Aph = 1.06 / 1.

Next, the prepared hologram recording medium sample was stored at 80 ° C. in a dry environment for 7 days. A portion of the hologram recording layer after storage was scraped off, and the sample thus scraped was subjected to infrared spectroscopic measurement in the same manner, and a characteristic absorption 1591 to 1592 cm ⁻¹ of the phenyl group of the Si-phenyl group, an intensity Bph of polyethylene glycol mono The ratio of the characteristic absorption of C = O bond of acrylate to the strength BC = O of 1726 to 1727 cm ^-1 was determined. BC = O / Bph = 1.02 / 1.

Residual amount of photopolymerizable compound after storage (%)
= [(BC = O / Bph) / (AC = O / Aph)] × 100 As a result, the residual amount of the photopolymerizable compound after storage was 96.2%.

Infrared spectroscopic measurement conditions are shown below.
Apparatus: Nicolet, Magna 760
Measuring method: One-time reflection ART method (diamond)
ST Japan Use DuraScope Resolution: 4cm ^-1
Integration count: 32

  The hologram recording medium sample of Example 1 showed excellent hologram recording characteristics.

[Comparative Example 1]
(Synthesis of matrix material)
To 5.0 g of diphenyldimethoxysilane (Ph ₂ Si (OMe) ₂ , manufactured by Shin-Etsu Chemical Co., Ltd.), a solution consisting of 0.37 mL of water, 0.15 mL of 2N hydrochloric acid aqueous solution, and 5.0 mL of the solvent 1-methoxy-2-propanol The mixture was added dropwise at room temperature while stirring, and stirring was continued for 1 hour to carry out a hydrolysis reaction. Thereafter, 5.82 g of tetraisopropoxytitanium (Ti (O—iPr) ₄ , manufactured by Azmax) was added to this reaction solution at room temperature, and then stirred at 80 ° C. for 1 hour to obtain a mixed solution. Ti / Si = 1/1 (molar ratio).

  To the obtained mixed solution, 0.75 mL of water and 1.5 mL of 1-methoxy-2-propanol were added at room temperature with stirring, and the stirring was continued for 1 hour, followed by further hydrolysis and condensation reaction. In this way, a sol solution was obtained.

  Using the obtained sol solution, a hologram recording medium was obtained in the same manner as in Example 1.

In the same manner as in Example 1, the produced hologram recording medium sample was stored at 80 ° C. in a dry environment for 7 days. When infrared spectroscopy was performed in the same manner as in Example 1,
Initial AC = O / Aph = 1.86 / 1
After storage BC = O /Bph=0.57/1
Met. The residual amount of the photopolymerizable compound after storage was 30.6%.

It is a figure which shows the schematic cross section of the hologram recording medium produced in the Example.

Explanation of symbols

(11): Hologram recording medium
(21): Hologram recording material layer
(22a) (23a): Antireflection film
(22) (23): Glass substrate
(24): Spacer

Claims (12)

A method for producing a hologram recording material comprising organic group-containing composite metal compound fine particles containing Si and another metal other than Si as a metal element, and a photopolymerizable compound,
Hydrolyzing and condensing a alkoxide compound of another metal other than Si to generate an oxide of the other metal;
Mixing the other metal oxide with a Si-containing material containing at least one selected from the group consisting of Si alkoxide compounds, silanol compounds, and condensates of these compounds;
A step of causing hydrolysis and condensation reaction of the Si-containing material to proceed, and a condensation reaction between a residual active group present in the oxide of the other metal and a silyloxy group of the Si-containing material;
Adding a photopolymerizable compound to the reaction system;
A method for producing a hologram recording material comprising:   The method for manufacturing a hologram recording material according to claim 1, wherein the metal other than Si is selected from the group consisting of Ti, Zr, Ta, Sn, Zn, and Al. Before hydrolysis of an alkoxide compound of another metal other than Si,
The method for producing a hologram recording material according to claim 1, further comprising a step of coordinating a ligand to an alkoxide compound of a metal other than Si.   The method for producing a hologram recording material according to claim 3, wherein the ligand is selected from the group consisting of a β-dicarbonyl compound, a polyhydroxylated ligand, and an α- or β-hydroxy acid. A step of hydrolyzing the Si alkoxide compound;
The method for manufacturing a hologram recording material according to claim 1, wherein the hydrolysis product is used as a Si-containing material. The Si alkoxide compound has the following general formula (I):
(R ₁₁ ) m Si (OR ₁₂ ) n (I)
(In the formula, R ₁₁ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₁₂ represents an alkyl group which may have a substituent. , M represents 1, 2 or 3, n represents 1, 2 or 3, provided that m + n is 4. R ₁₁ may be different depending on m, and R ₁₂ may be different depending on n. .)
The manufacturing method of the hologram recording material of any one of Claims 1-5 represented by these. The Si alkoxide compound is represented by the general formula (I):
R ₁₁ represents an aryl group which may have a substituent, R ₁₂ represents an alkyl group which may have a substituent, m represents 2, and n represents 2. Item 7. A method for producing a hologram recording material according to Item 6. The silanol compound has the following general formula (II):
(R ₂₁ ) j Si (OH) k (II)
(In the formula, R ₂₁ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, j represents 1, 2 or 3, provided that j + k is 4. R ₂₁ may be different depending on j.)
The manufacturing method of the hologram recording material of any one of Claims 1-4 represented by these. In the general formula (II), the silanol compound is
The method for producing a hologram recording material according to claim 8, wherein R ₂₁ represents an aryl group which may have a substituent, j represents 2, and k represents 2.   The method for producing a hologram recording material according to claim 1, wherein the photopolymerizable compound is selected from (meth) acrylic acid esters.   The method for producing a hologram recording material according to claim 1, further comprising a step of adding a photopolymerization initiator to the reaction system.   The hologram recording material obtained by the manufacturing method of the hologram recording material of any one of Claims 1-11.

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