Compounds, methods of manufacturing thereof, polymerizable compositions, polymers, holographic recording media, optical materials, and optical components

Abstract

This invention relates to a compound represented by the following formula (1). This invention provides a compound with high refractive index and excellent polymerizability that can be used as a raw material for optical materials, etc. [In the formula, A represents a polymerizable group. L represents a branching (n+1) valence linking group. R1 represents an aromatic ring group that may have substituents. R2 represents a monovalent organic group that may have substituents. X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents, respectively. m represents an integer of 0 or 1. n represents an integer from 1 to 3. p represents an integer of 0 or 1. In the formula, two R1s can bond to each other at any position to form a ring structure. Wherein, R1 = R2, X1 = X2, and p = 1 do not all simultaneously hold true.]

Description

[Technical Field]

[0001] This invention relates to a compound with high refractive index, high transparency and excellent polymerizability, and a method for manufacturing the same. Furthermore, this invention relates to a holographic recording medium, optical material, and optical component using a polymeric composition comprising the compound or a polymer thereof. [Previous Technology]

[0002] Previously, glass was mostly used as the optical material. For example, in the case of optical lenses, even lenses with the same focal length can be made thinner if a high refractive index material is used, thus providing advantages such as lightweight design and increased freedom in optical path design. Furthermore, high refractive index optical lenses are also effective for miniaturization, high resolution, and wide-angle applications in optical imaging devices.

[0003] In recent years, plastics with higher transparency have attracted attention as optical materials to replace glass. Compared with glass, plastic materials have the following advantages, such as ease of weight reduction, ease of improving mechanical strength, and ease of processing and molding. With the development of related technologies, there is an ongoing demand to improve the performance of plastic optical materials. For example, materials for optical lens applications require easy polymerization (polymerizability), good curability, and a high refractive index of the polymer.

[0004] Prior to this, various resins have been developed to increase the refractive index. For example, 9,9-bis[4-(2-acryloxyethoxy)phenyl]pyroxene has been frequently used as a high-refractive-index acrylate. However, its viscosity is relatively high, and the refractive index of the monomer is around 1.62, which is not high enough (Patent Document 1). In order to increase the refractive index, in addition to introducing aromatic rings, it is also effective to introduce sulfur atoms into the molecule. For example, Patent Document 2 describes a diacrylate monomer having a pentaerythritol skeleton with 1 to 2 naphthio groups in one molecule. In this case, the refractive index is 1.62 to 1.65. Patent Document 3 describes an acrylate compound having a glycerol skeleton with 2 benzothiazole rings in one molecule. In this case, the refractive index is also 1.63. For applications requiring an ultra-high refractive index exceeding 1.65, these are insufficient.

[0005] Patent Documents 4 and 5 disclose ultra-high refractive index acrylate compounds having dibenzofuran or dibenzocarbazole and a refractive index exceeding 1.7. However, their solubility in various media is not sufficient, limiting the media in which they can be used.

[0006] Patent Document 6 relates to an optical material used in holographic recording media. Patent Document 6 describes a pentaerythritol-type (meth)acrylate compound having three aromatic rings as an ultra-high refractive index compound. These compounds achieve high refractive indices due to their structure having three identical high-refractive sites. However, sometimes sufficient polymerization performance cannot be obtained due to steric hindrance around the polymerizable group, resulting in reduced holographic recording characteristics.

[0007] [Patent Document 1] Japanese Patent Application Publication No. Hei 6-220131 [Patent Document 2] Japanese Patent Application Publication No. 2008-527413 [Patent Document 3] Japanese Patent Application Publication No. 2005-133071 [Patent Document 4] International Publication No. 2021 / 006011 [Patent Document 5] International Publication No. 2021 / 006012 [Patent Document 6] Japanese Patent Application Publication No. 2017-14213 [Summary of the Invention]

[0008] The object of the present invention is to provide a compound that can be used as an optical material or optical component and has the properties of high refractive index, high transparency and easy polymerization.

[0009] The inventors have discovered that polymerizable pentaerythritol-type compounds with different types of high refractive index sites are compounds that combine the characteristics of high refractive index, high transparency and easy polymerization, and polymerizable compositions and polymers using them have high refractive index and high transparency.

[0010] That is, the main idea of ​​the present invention is as follows.

[0011] [1] A compound represented by the following formula (1),

[0012] [Chemical 1]

[0013] [In the formula, A represents a polymerizable group. L represents a branchable (n+1) valence linking group. R1 represents an aromatic ring group that may have substituents. R2 represents an organic group with a valence of 1 that may have substituents. X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents, respectively. m represents an integer of 0 or 1. n represents an integer of 1 to 3. p represents an integer of 0 or 1. In the formula, two R1s can bond to each other at any position to form a ring structure. In the formula, R1 = R2, X1 = X2, and p = 1 will not all be true at the same time]. [2] The compound described in [1], wherein the number of polymerizable groups in the above formula (1) is 1. [3] The compound described in [1] or [2], wherein the above A is ethylene oxide, vinyl, allyl, or (meth)acrylyl. [4] The compound described in [3], wherein the above A is (meth)acrylyl. [5] The compound described in any one of [1] to [4], wherein R1 is a condensed aromatic ring group that may have substituents, or a monocyclic aromatic group substituted with an aromatic ring group. [6] The compound described in any one of [1] to [5], wherein R2 has a partial structure represented by the following formula (2).

[0014] [Chemical 2]

[0015] [In the formula, J represents a carbon atom that may have a substituent or a nitrogen atom that may have a substituent, and G represents a sulfur atom, an oxygen atom or a nitrogen atom that may have a substituent]. [7] A compound represented by the following formula (3),

[0016] [Chemical 3]

[0017] [In the formula, R1 represents an aromatic cyclic group that may have substituents. R2 represents a monovalent organic group that may have substituents. X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents. p represents an integer of 0 or 1. In the formula, the two R1s may bond to each other at any position to form a ring structure. In the formula, R1 = R2, X1 = X2, and p = 1 may not all be true at the same time]. [8] A method for manufacturing a compound as described in [7] is characterized by subjecting the aliphatic cyclic compound represented by the following formula (4) to a ring-opening reaction.

[0018] [Chemical 4]

[0019] [In the formula, R1 represents an aromatic cyclic group that may have substituents. X1 represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents. p represents an integer of 0 or 1. Z represents an aliphatic linker that may have substituents and can be branched. r represents an integer of 0 or 1. In the formula, two R1s may bond to each other at any position to form a ring structure]. [9] The method of manufacturing the compound as described in [8], wherein the aliphatic cyclic compound represented by the above formula (4) is the compound represented by the following formula (5) or formula (6).

[0020] [Chemical 5]

[0021] [In the formula, R1 represents an aromatic ring group that may have substituents. X1 represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents. p represents an integer of 0 or 1. In the formula, two R1s may bond to each other at any position to form a ring structure].

[10] A polymeric composition comprising a compound as described in any one of [1] to [6] and a polymerization initiator.

[11] A holographic recording medium comprising the polymeric composition as described in

[10] .

[12] A polymer formed by polymerizing the polymeric composition as described in

[10] .

[13] An optical material comprising the polymer as described in

[12] .

[14] An optical material comprising the polymer as described in

[12] .

[15] A high-capacity memory comprising the holographic recording medium as described in

[11] .

[16] An optical element obtained by holographic recording on the holographic recording medium as described in

[11] .

[17] An AR glasses comprising optical elements as described in

[16] . [Effects of the Invention]

[0022] This invention provides a high-refractive-index compound that combines high transparency and easy polymerization, which can be used as an optical material. The compound of this invention is particularly suitable as a hard coating for optical lenses or optical components, and as a reactive compound for use in holographic recording media. By using the compound of this invention, optical materials and optical components with high diffraction efficiency, high light transmittance, and low haze can be achieved.

Implementation Method

[0024] Hereinafter, embodiments of the present invention will be specifically described. The present invention is not limited to the following embodiments, and various modifications can be made within its scope. In the present invention, "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryl" is a general term for acrylonitrile and methacryl. In the present invention, "may have substituents" means that it may have one or more substituents. "Nitrogen atoms that may have substituents" also includes imine groups, etc., when there are no substituents.

[0025] 1. Regarding the compounds of the present invention, the compounds of the present invention are represented by the following formula (1).

[0026] [Chemical 6]

[0027] [In the formula, A represents a polymerizable group. L represents a branchable (n+1) valence linking group. R1 represents an aromatic ring group that can have substituents. R2 represents a monovalent organic group that can have substituents. X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that can have substituents, respectively. m represents an integer of 0 or 1. n represents an integer from 1 to 3. p represents an integer of 0 or 1. In the formula, two R1s can bond to each other at any position to form a ring structure. In the formula, R1 = R2, X1 = X2, and p = 1 will not all be true at the same time].

[0028] 1-1. Regarding the structure of the compound of formula (1), the compound of formula (1) has a pentaerythritol skeleton, and one of the four molecular chains bonded to the quaternary carbon atom has a polymerizable group. On the other hand, at least one of the remaining three molecular chains has a structure exhibiting a high refractive index. This can further improve the refractive index of the polymer. Also, in the compound represented by formula (1), two of the remaining three molecular chains have the same structure, and one has a different structure. This can further improve the transparency of the polymer. A different structure means that the molecular chain represented by -X2-R2 in formula (1) has a different structure than the molecular chain represented by -(X1)p-R1. Even if the elements, partial structures, and quantities constituting R1 and R2, X1 and X2 are the same, but their bonding positions are different, -X2-R2 is considered to be a different structure relative to -(X1)p-R1.

[0029] 1-2. Regarding AA in formula (1), which is a polymerizable group, its structure is not particularly limited. Examples of polymerizable groups include: (meth)acrylic, allyl, vinyl, vinyl-substituted phenyl, isopropenyl-substituted phenyl, vinyl-substituted naphthyl, isopropenyl-substituted naphthyl, ethylene oxide, 2-methylethylene oxide, oxacyclobutyl, etc., and the group suitable for the target polymerization method can be selected. In photopolymerization using a photopolymerization initiator, ethylene oxide, vinyl, allyl, and (meth)acrylic are preferred. Among them, (meth)acrylic is particularly preferred due to its higher reactivity.

[0030] 1-3. In formula (1), LL represents a branchable (n+1) valence linker. L does not necessarily have to contain heteroatoms, but from the point of view of ease of synthesis, it is preferable to have oxygen atoms, sulfur atoms, or nitrogen atoms that may have substituents.

[0031] Based on the consideration of the high solubility of the compound of formula (1) in various media and the avoidance of staining, L is preferably an aliphatic hydrocarbon group having an oxygen atom, a sulfur atom, or a nitrogen atom that may have a substituent. The number of carbons of the aliphatic hydrocarbon group (excluding the number of carbons of the substituent) is preferably 1 to 8. If the number of carbons of the aliphatic hydrocarbon group is 8 or less, the refractive index of the compound of formula (1) is not easily reduced, and the viscosity is reduced due to the smaller molecular weight, thereby improving processability. The aliphatic hydrocarbon group constituting L can be either a cyclic aliphatic hydrocarbon group or a chain aliphatic hydrocarbon group, or such structures can be combined. Based on the consideration of mitigating the steric hindrance around the polymerizable group A, a chain aliphatic hydrocarbon group is preferred.

[0032] Examples of chain-like aliphatic hydrocarbon groups having oxygen atoms, sulfur atoms, or nitrogen atoms that may have substituents, constituting L, when n=1, include: oxymethylene, oxyethyl, 1,3-oxypropyl, 1,2-oxypropyl, oxybutyl, 2-hydroxyoxypropyl, oxyhexyl, oxyheptyl, 3-oxypentyl, -OCH2CH2NHC(O)-, -OCH2CH2OCH2CH2NHC(O)-, -OCH2CH2SCH2CH2-, -OCH2CH2NHC(S)-, -OCH2CH2OCH2CH2NHC(S)-, -OCH2CH2SCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, etc. L may also be a combination of two or more of these groups. Examples of L when n = 2 or 3 include: -(OCH2)2C(CH3)NHC(O)-, and a linking group in which any hydrogen atom in the above-mentioned chain aliphatic hydrocarbon group is replaced by a linking group that bonds with the polymerizable group A. In this case, it can also bond with the polymerizable group through a branched structure.

[0033] From the perspective of high refractive index, L is preferably a cyclic group. The rings contained in the cyclic group constituting L can be monocyclic or condensed ring structures. The number of rings contained in L is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. The rings contained in L do not necessarily need to be aromatic, but in order to maintain a small size in the overall molecule and maintain a high refractive index, they are preferably aromatic hydrocarbon rings. Examples of aromatic hydrocarbon rings constituting L include: benzene rings, indene rings, naphthalene rings, azurite rings, fumonisin rings, acenaphthene rings, anthracene rings, phenanthrene rings, pyrene rings, etc.

[0034] L may have substituents. Examples of substituents that L may have include: halogen atoms (chlorine atoms, bromine atoms, iodine atoms), hydroxyl groups, mercapto groups, alkyl groups with 1 to 8 carbon atoms, alkenyl groups with 2 to 8 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, phenyl groups, tolyl groups, naphthyl groups, cyano groups, acetoxy groups, alkyl carbonyl groups with 2 to 9 carbon atoms, alkoxy carbonyl groups with 2 to 9 carbon atoms, amine sulfonyl groups, alkylamine sulfonyl groups with 2 to 9 carbon atoms, alkyl carbonyl groups with 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetaminoyl groups, dialkylaminoethyl groups bonded with alkyl groups with 1 to 4 carbon atoms, trifluoromethyl groups, alkylthio groups with 1 to 8 carbon atoms, aromatic cyclothio groups with 6 to 10 carbon atoms, nitro groups, etc.

[0035] 1-4. Regarding X1 and X2 in formula (1), X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents. From the viewpoint of suppressing water absorption to a lower level, X1 and X2 are preferably oxygen atoms or sulfur atoms, and more preferably sulfur atoms that impart a high refractive index. There are no particular restrictions on the group that can be substituted for a nitrogen atom, but it is preferred to be an alkyl group with 1 to 8 carbons such as methyl or ethyl, or an aromatic hydrocarbon group such as phenyl or naphthyl.

[0036] 1-5. Regarding R1 in formula (1), R1 represents an aromatic ring group that may have substituents. The aromatic ring constituting R1 is generally divided into aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetraphenylene ring, pyrene ring, benzo[a]pyrene ring, ring, biphenyl ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fumonisin ring. Examples of aromatic heterocycles include: furan rings, benzofuran rings, dibenzofuran rings, naphthofuran rings, benzonaphthofuran rings, dinaphthofuran rings, thiophene rings, benzothiophene rings, dibenzothiophene rings, naphthothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, pyrrole rings, indole rings, carbazole rings, benzocarbazole rings, dibenzocarbazole rings, pyridine rings, quinoline rings, isoquinoline rings, etc., containing one heteroatom; imidazole rings, triazole rings, tetraazole rings, oxyazole rings, thiazole rings, pyrazine rings, pyrazine rings, triazole rings, thiadiazole rings, etc., containing two or more heteroatoms; benzooxyazole rings, thiophene oxyazole rings, etc. Ring, thiazo[a]azole ring, thiazo[a]azole ring, thiazo[a]imidazole ring, thiazo[a]pyridine ring, thiazo[a]pyrimidine ring, thiazo[a]pyridine ring, naphtho[a]azole ring, hydroxyquinoline[a]azole ring, di[a]azole[a]pyridine ring, phen[a]azole ring, benzo[a]thiazole ring, fluorothiazole ring, thieno[a]thiazole ring, thiazo[a]thiazole ring, thiazole Rings formed by the condensation of two or three rings of aromatic heterocycles containing two or more heteroatoms, including imidazole ring, thienothiadiazole ring, thiazonothiadiazole ring, thiazonopyridine ring, thiazonopyridine ring, thiazonopyridine ring, naphthothiazolium ring, hydroxyquinolinethiazolium ring, thiazolyl ...

[0037] The aromatic hydrocarbon ring constituting R1 is preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, tandem benzene ring, or genus ring, based on its ease of synthesis and availability. Based on the viewpoint of fluorescence suppression of the compound of formula (1), the aromatic hydrocarbon ring constituting R1 is more preferably a benzene ring, naphthalene ring, tandem benzene ring, or genus ring.

[0038] As the aromatic heterocycle constituting R1, it is preferably a sulfur-containing aromatic heterocycle, which tends to increase the refractive index of the compound of formula (1). The sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the aromatic heterocycle. As a heteroatom, in addition to a sulfur atom, it may also have an oxygen atom, a nitrogen atom, or both an oxygen atom and a nitrogen atom. Considering the avoidance of staining and the assurance of solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2. As sulfur-containing aromatic heterocycles, thiophene rings, benzothiophene rings, dibenzothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, thiaran rings, naphthothiophene rings, dinaphthothiophene rings, dibenzothiaran rings, etc., are aromatic heterocycles containing one sulfur atom; thiam rings, etc., are aromatic heterocycles containing two or more sulfur atoms; thiazole rings, isothiazole rings, benzothiazole rings, naphthothiazole rings, phenanthrene rings, thiazole imidazole rings, thiazole pyridine rings, thiazole pyridine rings, thiazole pyridine rings, diazopyridine rings, thiazole pyridine rings, thiazole pyridine rings, thiazole pyridine rings, dibenzothiophene rings, thiazole pyridine rings, thiazole pyridine rings, dibenzothiophene rings, thiazole pyridine rings, thiazole pyridine rings, thiazole pyridine rings, etc., are aromatic heterocycles containing two or more types of heteroatoms. Sulfur-containing aromatic heterocycles can be monocyclic or condensed rings. From the perspective of increasing refractive index, condensed rings are preferred. The number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and especially preferably 2 to 5, considering the ease of obtaining raw materials or the ease of synthesis. Particularly from the perspective of increasing refractive index and low colorability, sulfur-containing aromatic heterocycles are preferably benzothiazole rings, dibenzothiphene rings, benzothiphene rings, benzonaphthothiphene rings, dinaphthothiphene rings, or thion rings.

[0039] As an aromatic heterocycle constituting R1, it can also be a nitrogen-containing aromatic heterocycle, based on the viewpoint of ease of synthesis. The nitrogen-containing aromatic heterocycle has at least a nitrogen atom as a heteroatom constituting the aromatic heterocycle. In addition to a nitrogen atom, it may also have an oxygen atom, a sulfur atom, or both oxygen and sulfur atoms. From the perspective of avoiding coloration, the number of heteroatoms constituting the nitrogen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2. Examples of nitrogen-containing aromatic heterocycles include: pyrrole rings, indole rings, carbazole rings, benzo[a]carbazole rings, dibenzo[a]carbazole rings, pyridine rings, quinoline rings, isoquinoline rings, acetazole rings, thiazole rings, benzo[a]acetazole rings, naphtho[a]acetazole rings, benzo[a]thiazole rings, naphtho[a]thiazole rings, phenanthrene rings, phenanthrene-thiazole rings, thieno[a]acetazole rings, thiazo[a]acetazole rings, fluorothiazole rings, thieno[a]thiazole rings, and thiazo[a]thiazole rings, etc., aromatic heterocycles containing one nitrogen atom; imidazole rings, triazole rings, tetraazole rings, etc. Aromatic heterocycles containing two or more nitrogen atoms, including azole rings, pyridine rings, pyridine rings, triazole rings, thiadiazole rings, benzimidazole rings, azidoimidazole rings, azidopyridine rings, azidotazoline rings, azidopyrimidine rings, azidopyridine rings, hydroxyquinoline azidoazole rings, diazidopyridine rings, thiazolineimidazole rings, thiazolinethiadiazole rings, thiazolinepyridine rings, thiazolinetazoline rings, thiazolinepyrimidine rings, thiazolinepyridine rings, and hydroxyquinolinethiazolium rings.

[0040] The nitrogen-containing aromatic heterocycle can be a monocyclic ring or a condensed ring. From the perspective of increasing refractive index, a condensed ring is preferred. The number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and especially preferably 2 to 5, considering the ease of obtaining raw materials or the ease of synthesis. Particularly from the perspective of increasing refractive index and low colorability, the nitrogen-containing aromatic heterocycle is preferably a carbazole ring, a benzo[a]carbazole ring, a dibenzo[a]carbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a benzo[a]carbazole ring, a benzo[a]thiazole ring, a benzimidazole ring, or a thiadiazole ring, and more preferably a carbazole ring, a benzo[a]carbazole ring, a dibenzo[a]carbazole ring, a benzo[a]carbazole ring, a benzo[a]thiazole ring, a benzimidazole ring, or a thiadiazole ring.

[0041] The aromatic heterocycle constituting R1 can also be an oxygen-containing aromatic heterocycle. This tends to improve the heat resistance or weather resistance of polymers made from compounds of formula (1). The oxygen-containing aromatic heterocycle has at least an oxygen atom as a heteroatom constituting the aromatic heterocycle. In addition to oxygen atoms, it can also have nitrogen atoms, sulfur atoms, or both. For the purpose of ensuring heat resistance, the number of oxygen atoms constituting the oxygen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2. Examples of oxygen-containing aromatic heterocycles include: furan ring, benzofuran ring, dibenzofuran ring, naphthofuran ring, benzonaphthofuran ring, dinaphthofuran ring, phenazonium ring, acetazole ring, isoazonium ring, benzoazonium ring, benzoisoazonium ring, benzoisoazonium ring, naphthoazonium ring, thienoazonium ring, thiazonoazonium ring, acezonoimidazole ring, and fluorothiazonoazonium ring, which contain one oxygen atom; and dibenzodioxane-hexene ring, acezonoazonium ring, and diacezonopyridine ring, which contain two or more oxygen atoms.

[0042] The oxygen-containing aromatic heterocycle can be a monocyclic ring or a condensed ring. From the perspective of increasing refractive index, a condensed ring is preferred. The number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and especially preferably 2 to 5, considering the ease of obtaining raw materials or the ease of synthesis. Particularly from the perspective of increasing refractive index and low colorability, the oxygen-containing aromatic heterocycle is preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, an oxazole ring, an isooxazole ring, a benzooxazole ring, a benzoisooxazole ring, a benzooxazole ring, and a naphthooxazole ring, more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, and a benzooxazole ring.

[0043] The aromatic ring constituting R1 may have substituents. Examples of substituents include: halogen atoms such as chlorine, bromine, and iodine; alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkoxy groups, cyano groups, acetoxy groups, alkyl carbonyl groups having 2 to 9 carbon atoms, alkoxy carbonyl groups having 2 to 9 carbon atoms, amine sulfonyl groups, alkylamine sulfonyl groups having 2 to 9 carbon atoms, alkyl carbonyl groups having 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetamino groups, dialkylaminoethyl groups formed by alkyl groups having 1 to 4 carbon atoms, trifluoromethyl groups, alkylthio groups having 1 to 8 carbon atoms, aromatic ring thio groups having 6 to 10 carbon atoms, and nitro groups. Examples of such groups include: alkyl groups with 1 to 8 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkylthio groups with 1 to 8 carbon atoms, aromatic cyclothio groups with 6 to 10 carbon atoms, cyano groups, acetoxy groups, alkyl carboxyl groups with 2 to 8 carbon atoms, amine sulfonyl groups, alkylamine sulfonyl groups with 2 to 9 carbon atoms, and nitro groups.

[0044] Regarding the aromatic rings constituting R1, from the viewpoint of increasing the refractive index of the compound of formula (1), it is preferable to further have a group containing an aromatic ring as a substituent. The aromatic ring contained in the substituent is synonymous with the aromatic ring constituting R1. The aromatic ring contained in the substituent may be directly bonded to the aromatic ring constituting R1 at any position, or may be bonded to the aromatic ring constituting R1 via an oxygen atom, a sulfur atom, or a nitrogen atom that may have a substituent, or may be bonded to the aromatic ring constituting R1 via any linking group. The substituent is more preferably directly bonded.

[0045] Furthermore, by setting the aromatic ring contained in the substituent as a sulfur-containing aromatic heterocycle, there is a tendency to increase the refractive index of the compound of formula (1). The definition of a sulfur-containing aromatic heterocycle is synonymous with that of a sulfur-containing aromatic heterocycle in R1. As a sulfur-containing aromatic heterocycle, it is more preferably a condensation ring, and even more preferably a benzothiazole ring, a dibenzothiphene ring, a benzothiphene ring, a benzonaphthothiphene ring, a dinaphthothiphene ring, or a thione ring.

[0046] There is no particular limitation on the number of aromatic rings of the substituent of R1. From the point of view of ease of synthesis and solubility, it is preferred to be 1 to 4, and even more preferably 1 to 2.

[0047] Regarding the aromatic ring constituting R1, based on the viewpoint of taking into account both high refractive index and high solubility in various media, it is preferable to be a condensed aromatic ring that may have substituents, or a monocyclic aromatic ring substituted with an aromatic ring group, and more preferably a condensed aromatic heterocycle that may have substituents, or an aromatic hydrocarbon ring with an aromatic heterocycle as a substituent.

[0048] The aromatic ring constituting R1 may have two or more of the above-mentioned sulfur-containing aromatic heterocycles, nitrogen-containing aromatic heterocycles, and oxygen-containing aromatic heterocycles. For example, the aromatic ring constituting R1 may also be a carbazole ring with a dibenzothiophene ring as a substituent. Compounds of formula (1) with this structure often have a high refractive index.

[0049] When p=1, the aromatic ring constituting R1 can be bonded to X1 in formula (1) at any position. When p=0, the aromatic ring constituting R1 can be bonded to the pentaerythritol skeleton in formula (1) at any position.

[0050] In order to maintain a small size in the overall molecular structure and achieve a higher refractive index, the two R1s in formula (1) are preferably bonded to each other at any position to form a ring structure. On the other hand, in order to maintain the overall flexibility of the molecular structure and achieve higher solubility in various media, the two R1s in formula (1) are preferably not bonded to each other.

[0051] 1-6. Regarding R2 in formula (1), R2 represents a monovalent organic group. R2 can be any of the linear, branched, or cyclic forms. Furthermore, these structures can be combined according to the physical properties required by the compound of formula (1). As long as -X2-R2 in formula (1) is a different structure as described above, R2 can be a structure selected from R1 above, or it can be the same as R1.

[0052] From the viewpoint of increasing the refractive index of the compound of formula (1), R2 preferably has a ring structure. The ring structure can be a monocyclic structure or a condensed ring structure. From the viewpoint of the high solubility of the compound of formula (1) in various media, the number of rings constituting R2 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. The ring constituting R2 does not necessarily need to be aromatic, but from the perspective of maintaining a small size in the overall molecule while achieving a high refractive index, it is preferable to have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the ring structure.

[0053] Examples of aromatic hydrocarbon rings constituting R2 include: benzene ring, indene ring, naphthalene ring, azurite ring, fusine ring, acenaphthene ring, anthracene ring, phenanthrene ring, pyrene ring, etc. Examples of aromatic heterocycles constituting R2 include: furan rings, benzofuran rings, dibenzofuran rings, naphthofuran rings, benzonaphthofuran rings, dinaphthofuran rings, thiophene rings, benzothiophene rings, dibenzothiophene rings, naphthothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, pyrrole rings, indole rings, carbazole rings, pyridine rings, quinoline rings, isoquinoline rings, etc., containing one heteroatom; imidazole rings, triazole rings, tetraazole rings, oxyazole rings, thiazole rings, pyrazine rings, pyridine rings, triazole rings, thiadiazole rings, etc., containing two or more heteroatoms; benzooxyazole rings, thiophene-oxyazole rings, thiazole rings... Rings including benzo[a]azole ring, benzo[a]azole ring, benzo[a]imidazole ring, benzo[a]pyridine ring, benzo[a]pyrimidine ring, benzo[a]pyridine ring, naphtho[a]azole ring, hydroxyquinoline[a]azole ring, di[a]azole[a]pyridine ring, phen[a]azole ring, benzo[a]thiazole ring, fluorothiazole ring, thieno[a]thiazole ring, thieno[a]thiazole ring, thieno[a]imidazolium ring, thieno[a]thiadiazole ring, thieno[a]thiadiazole ring, thieno[a]pyridine ring, thieno[a]pyrimidine ring, thieno[a]pyridine ring, naphtho[a]thiazole ring, hydroxyquinolinethiazole ring, thiazoline ring, and phen[a]thiazoline ring, including rings formed by the condensation of two or three rings of aromatic heterocycles containing two or more heteroatoms.

[0054] Based on the viewpoint of the ease of synthesis of the compound of formula (1), R2 is preferably a heterocyclic structure, and more preferably a structure containing an azole ring as a nitrogen-containing 5-membered ring.

[0055] Examples of azole rings include: pyrrole rings containing one nitrogen atom, thiazole rings containing two or more heteroatoms, oxazole rings, imidazole rings, pyrazole rings, triazole rings, furazolidone rings, thiadiazole rings, tetraazole rings, etc. For the purpose of efficiently obtaining the target compound, R2 is preferably a partial structure represented by the following formula (2).

[0056] [Chemical 7]

[0057] [In the formula, J represents a carbon atom that may have a substituent or a nitrogen atom that may have a substituent, and G represents a sulfur atom, an oxygen atom or a nitrogen atom that may have a substituent].

[0058] The partial structure represented by formula (2) may be appropriately selected as needed. Based on the ease of synthesis of the compound of formula (1) or its high solubility in various media, it is preferred to be a thiazole ring, a thiazole ring, an imidazole ring, or a thiadiazole ring.

[0059] As described above, from the viewpoint of increasing the refractive index of the compound of formula (1), R2 is preferably an aromatic heterocycle, but more preferably a condensed aromatic heterocycle. Examples of condensed aromatic heterocycles that R2 may have include: indole rings, benzothiazole rings, benzoxazole rings, benzimidazole rings, etc. Considering the tendency to balance the high refractive index and high solubility of the compound of formula (1), a benzothiazole ring is particularly preferred.

[0060] The ring structure of R2 described above can be directly bonded to X2 at any position, or it can be bonded to X2 via an aliphatic linker that may have substituents. Considering the improved solubility of the compound of formula (1) in various media, the aliphatic linker is preferably chain-like. By partially setting the chain-like portion as an aliphatic hydrocarbon group, there is a tendency to further improve its solubility. In this case, the number of carbons (excluding the number of carbons of the substituents) is preferably 1 to 8. By making the number of carbons 8 or less, there is a tendency to make the refractive index less likely to decrease, and the viscosity is easier to decrease due to the smaller molecular weight, thereby improving processability. Examples of aliphatic linker groups include: methylene, ethyl, propyl, carbonyl, thiocarbonyl, -OC(O)-, -NHC(O)-, -OC(S)-, -NHC(S)-, -CH2OC(O)-, -CH2CH2OC(O)-, -CH2CH2OCH2CH2OC(O)-, -CH2CH2SCH2CH2OC(O)-, -CH2OC(S)-, -CH2CH2OC(S)-, -CH2CH2OCH2CH2OC(S)-, -CH2CH2SCH2CH2OC(S)-, -CH2 SC(O)-, -CH2CH2SC(O)-, -CH2CH2OCH2CH2SC(O)-, -CH2CH2SCH2CH2SC(O)-, -CH2NHC(O)-, -CH2NHC(S)-, -CH2CH2NHC(O)-, - CH2CH2NHC(S)-, -CH2CH2OCH2CH2NHC(O)-, -CH2CH2OCH2CH2NHC(S)-, -CH2CH2SCH2CH2NHC(O)-, -CH2CH2SCH2CH2NHC(S)-, etc.

[0061] Furthermore, the ring structure of R2 may have substituents. Examples of substituents that R2 may have include: halogen atoms such as chlorine, bromine, and iodine; alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, aromatic hydrocarbon rings having 1 to 14 carbon atoms, aromatic heterocycles, alkoxy groups, cyano groups, acetoxy groups, alkyl carbonyl groups having 2 to 9 carbon atoms, alkoxy carbonyl groups having 2 to 9 carbon atoms, amine sulfonyl groups, alkylamine sulfonyl groups having 2 to 9 carbon atoms, alkyl carbonyl groups having 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetaminoyl groups, dialkylaminoethyl groups formed by alkyl groups having 1 to 4 carbon atoms, trifluoromethyl groups, alkylthio groups having 1 to 8 carbon atoms, aromatic ring thio groups having 6 to 10 carbon atoms, and nitro groups. Among these, considering ease of acquisition, the following are preferably examples: alkyl groups with 1 to 8 carbon atoms, aromatic hydrocarbon rings with 1 to 14 carbon atoms, aromatic heterocycles, alkoxy groups with 1 to 8 carbon atoms, cyano groups, acetoxy groups, alkyl carboxyl groups with 2 to 8 carbon atoms, amine sulfonyl groups, alkylamine sulfonyl groups with 2 to 9 carbon atoms, and nitro groups. Furthermore, when R2 has a ring structure, from the viewpoint of increasing the refractive index of the compound of formula (1), a group that further contains an aromatic ring can also be appropriately selected as a substituent. The aromatic ring contained in the substituent is synonymous with the aromatic ring constituting R1. The aromatic ring contained in these substituents can be directly bonded to the ring structure of R2 at any position, or can be bonded to the ring structure of R2 via an oxygen atom, a sulfur atom, or a nitrogen atom that may have a substituent, or can be bonded to the ring structure of R2 via any linking group. It is more preferable that the substituent is directly bonded to the ring structure of R2.

[0062] 1-7. Regarding the expression (1), m and nm represent integers of 0 or 1. The expression m can be appropriately selected. From the viewpoint of mitigating the steric hindrance around the polymerizable group A and improving the reactivity of the compound of expression (1), m = 1 is preferred.

[0063] n represents an integer from 1 to 3. The choice of n is also appropriate. For example, considering the ease of polymerization of the compound in formula (1), n ​​can be set to 2 or 3. On the other hand, considering the tendency to achieve higher refractive index, the compound in formula (1) is preferably a monofunctional compound with fewer polymerizable elements, and more preferably a monofunctional compound with a polymerizable element of 1. That is, considering the high refractive index, n is preferably 1 or 2, and more preferably n = 1.

[0064] 1-8. Molecular weight: Based on the viewpoint of suppressing viscosity and maintaining good processability, the compound of formula (1) preferably has a molecular weight of 2000 or less, more preferably 1500 or less. In terms of reducing shrinkage during polymerization, the compound of formula (1) preferably has a molecular weight of 400 or more, more preferably 500 or more, and even more preferably 550 or more.

[0065] 1-9. Relationship between molecular structure and physical properties A compound of formula (1) has one polymerizable group in one of the four molecular chains of a pentaerythritol backbone, and at least one of the remaining three molecular chains exhibits a high refractive index structure, thereby it can be used as a polymerizable compound (monomer) with a high refractive index. In particular, by appropriately introducing a high refractive index site with a heterogeneous structure as described above, it is possible to simultaneously ensure the high solubility of the monomer in various media and adjust the compatibility of the polymer with the medium after polymerization. For example, a high refractive index is achieved using molecular chain -(X1)p-R1. High compatibility in the target medium is ensured using molecular chain -X2-R2. This allows for the acquisition of a high refractive index and high transparency polymer with low haze.

[0066] 1-10. Examples of Compounds Specific examples of compounds represented by the above formula (1) are illustrated below. The compounds of the present invention are not limited to these, provided that they do not depart from the spirit of the invention.

[0067] [Chemical 8]

[0068] [Chemical 9]

[0069] [Chemical 10]

[0070] [Chemical 11]

[0071] [Chemical 12]

[0072] [Chemical 13]

[0073] 1-11. Regarding the synthetic method, the compound of formula (1) can be synthesized by combining various known methods. For example, it can be synthesized by reacting the compound represented by the following formula (3) with a compound having a group that can react with a hydroxyl group.

[0074] [Chemical 14]

[0075] [In the formula, R1 represents an aromatic cyclic group that may have substituents. R2 represents a monovalent organic group that may have substituents. X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents, respectively. p represents an integer of 0 or 1. In the formula, the two R1s can bond to each other at any position to form a ring structure. In the formula, R1 = R2, X1 = X2, and p = 1 will not all be true at the same time].

[0076] An example of the synthesis of the compound of formula (1) will be described below.

[0077] [Chemical 15]

[0078] For example, the compound of formula (1) is a compound (1A) in which the polymerizable group A of formula (1) is (meth)acrylic. Compound (1A) can be manufactured by reacting the hydroxyl group of the compound of formula (3) above with a (meth)acrylic esterifying agent equivalent to compound (a).

[0079] The (meth)acrylate esterifying agent can be any compound having a (meth)acrylic acid group or a group that can be converted to a (meth)acrylic acid group and can react with the active hydrogen of the hydroxyl group in formula (3). Examples of (meth)acrylate esterifying agents include: (meth)acrylate chloride, (meth)acrylate anhydride, (meth)acrylate, 3-chloropropionic acid chloride, 2-acryloxyethyl isocyanate, 2-methacryloxyethyl isocyanate, 2-(2-methacryloxyethoxy)ethyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate, etc.

[0080] The reaction of the active hydrogen of the hydroxyl group in formula (3) with the (meth)acrylate esterifying agent can be carried out using known methods. For example, the compound of formula (3) can be reacted with the (meth)acrylate esterifying agent in the presence of a basic compound to obtain compound (1A).

[0081] The basic compound may be one or more organic basic compounds (triethylamine, pyridine, imidazole, etc.), or one or more inorganic basic compounds (sodium carbonate, potassium carbonate, etc.), or one or more organic basic compounds may be combined with one or more inorganic basic compounds.

[0082] In the reaction of the compound of formula (3) with the (meth)acrylate esterifying agent, it is preferable to use an organic solvent. Examples of organic solvents include dimethoxyethane, dichloromethane, tetrahydrofuran (THF), toluene, N,N-dimethylformamide (DMF), etc. The organic solvent may be one type or two or more types may be used together.

[0083] In the manufacture of compound (1A), it is preferable to purify the reactants (crude product) obtained in the synthesis reaction. Purification removes impurities, thus achieving low staining. Known methods can be used for purification. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods can be implemented individually or in combination.

[0084] When compound (1A) is a solid at room temperature, recrystallization is preferred in order to facilitate the removal of coloring substances.

[0085] Examples of recrystallization solvents include: aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, tert-butyl methyl ether, and 1,4-dimethyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, 2-methoxyethanol, 2-butoxyethanol, and propylene glycol monomethyl ether; diols such as ethylene glycol and diethylene glycol; and water. One of these solvents may be used alone, or two or more may be used in combination.

[0086] The compound of formula (3) can be manufactured by combining various known methods.

[0087] For example, although there are cases with low yield and large loading for single purification, the compound of formula (3) can be synthesized by simultaneously or sequentially linking the following compounds (c-1) and (c-2) with high refractive index sites through nucleophilic substitution reaction to pentaerythritol trihalide (b).

[0088] [Chemical 16]

[0089] The compound of formula (3) can be synthesized in high yield by using the ring-opening reaction of the aliphatic cyclic compound represented by formula (4) below.

[0090] [Chemical 17]

[0091] [In the formula, R1 represents an aromatic cyclic group that may have substituents. X1 represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents. p represents an integer of 0 or 1. Z represents an aliphatic linker group that may have substituents and can branch. r represents an integer of 0 or 1. In the formula, two R1s can bond to each other at any position to form a ring structure].

[0092] Here, when r = 0, formula (4) is an oxacyclobutane compound.

[0093] When r = 1, Z represents an aliphatic linker that can have substituents and can be branched. Examples of aliphatic cyclic compounds of formula (4) include: cyclic carbonate compounds, cyclic aminocarbamate compounds, cyclic thiocarbonate compounds, cyclic thioaminocarbamate compounds, cyclic sulfate compounds, cyclic sulfite compounds, cyclic phosphate compounds, etc.

[0094] When manufacturing the compound of formula (3), the aliphatic cyclic compound of formula (4) may be selected as appropriate as needed. Considering that a compound with both high refractive index and high solubility can be obtained, the aliphatic cyclic compound of formula (4) is preferably an oxetane compound represented by formula (5) below, or a cyclic carbonate compound represented by formula (6) below.

[0095] [Chemical 18]

[0096] [In the formula, R1 represents an aromatic cyclic group that may have substituents. X1 represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents. p represents an integer of 0 or 1. In the formula, two R1s can bond to each other at any position to form a ring structure].

[0097] <Example of synthesis of aliphatic cyclic compound of formula (4) with r=1> As shown in the following reaction formula, any one of the following reagents (d) – cyclic carbonate esterifying reagent, cyclic aminocarbamate esterifying reagent, cyclic thiocarbonate esterifying reagent, cyclic thioaminocarbamate esterifying reagent, cyclic sulfate esterifying reagent, cyclic sulfite esterifying reagent, and cyclic phosphorylation esterifying reagent – ​​is applied to pentaerythritol trihalide (b) to obtain intermediate (e). Then, a compound (c-1) with a high refractive index is attached to intermediate (e) to synthesize aliphatic cyclic compound of formula (4).

[0098] Compound (f) is applied to intermediate (e) to pre-introduce part of the structure of the high refractive site, and the obtained intermediate (g) is combined with compound (h), thereby synthesizing the aliphatic cyclic compound of formula (4).

[0099] By linking a compound (c-1) with a high refractive index to pentaerythritol dihalide (i) to replace pentaerythritol trihalide (b), an intermediate (j) is obtained. The intermediate (j) is then reacted with reagent (d) to synthesize the aliphatic cyclic compound of formula (4).

[0100] The compound (c-2) with a high refractive index site is reacted with the aliphatic cyclic compound of formula (4) to introduce the high refractive index site while opening the aliphatic cyclic structure, thereby synthesizing the compound of formula (3).

[0101] The compound of formula (3) can also be synthesized by directly bonding the high refractive index site (c-2) to the intermediate (j).

[0102] [Chemistry 19]

[0103] <Example of synthesis of aliphatic cyclic compound of formula (4) with r=0> In this case, the aliphatic cyclic compound of formula (4) is the oxetane compound represented by formula (5). As shown in the following reaction formula, the aliphatic cyclic compound of formula (4) can be synthesized, for example, by forming an oxetane structure from pentaerythritol trihalide (b) under acidic or basic conditions, thereby obtaining an intermediate (k), and then linking it to a compound (c-1) with a high refractive index site.

[0104] Compound (f) is applied to intermediate (k) to introduce a portion of the structure of the high refractive index region in advance, so that the obtained intermediate (l) is combined with compound (h), thereby synthesizing compound (5).

[0105] By reacting the compound (c-2) with the compound of formula (5), the high refractive index site can be introduced at the same time as the ring-opening of the oxobutane structure, thereby synthesizing the compound of formula (3).

[0106] [Chemical 20]

[0107] 2. Regarding the polymerizable composition of the present invention, the polymerizable composition of the present invention contains a compound of formula (1) and a polymerization initiator. By means of the polymerization initiator, the polymerizable functional group A of the compound of formula (1) undergoes a polymerization reaction, thereby obtaining the polymer of the present invention.

[0108] 2-1. Polymerization Initiator There is no particular limitation on the type of polymerization initiator; it can be appropriately selected from known polymerization initiators depending on the polymerization method. Furthermore, there is no limitation on the polymerization method; polymerization can be carried out using known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and partial polymerization.

[0109] Examples of polymerization initiators included in the polymerizable compositions of the present invention include: free radical polymerization initiators, redox polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. Furthermore, photocationic polymerization initiators that generate cations as active species through light irradiation may also be used. Moreover, the examples of polymerization initiators described below also include those commonly referred to as polymerization catalysts.

[0110] 2-1-1. Free Radical Polymerization Initiator <Photopolymerization Initiator> Regarding the photopolymerization initiator that assists in the polymerization of the polymerizable composition of the present invention, any known photofree radical polymerization initiator may be used. Examples include azo compounds, azido compounds, organic peroxides, organoborates, onium salts, imidazolium derivatives, titanocene compounds, iodinated salts, organothiols, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, 9-oxosulfuronide compounds, anthraquinones, ketals, phosphine oxides, sulfonyl compounds, carbamate derivatives, sulfonamides, triarylethanols, and oxime esters. Among these, benzophenones, phosphine oxides, and oxime esters are preferred as photopolymerization initiators, considering compatibility and ease of acquisition.

[0111] Specific examples of photopolymerization initiators include: benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, tributylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligomer {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzoin dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-hydroxylinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-hydroxylinyl)phenyl (2,4,6-Trimethylbenzyl)-Butanone-1, Diethyl-9-oxosulfuron, Isopropyl-9-oxosulfuron, 2,4,6-Trimethylbenzyldiphenylphosphine oxide, Bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionic acid)benzyl]phenyl}-2-methylpropane-1-one and methyl benzoate, 1-[4-(phenylthio)-2-(O-benzoyl oxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]-1-(O-acetylgoxy)acetone, etc.

[0112] Any one of these photopolymerization initiators may be used alone, or two or more may be used together in any combination and ratio.

[0113] Regarding the content of the photopolymerization initiator in the polymerizable composition of the present invention, when the total amount of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass, it is generally 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass or more. Its upper limit is generally 10 parts by mass or less, preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. If too much photopolymerization initiator is added, polymerization may proceed rapidly, which may not only increase the birefringence of the hardened body but also worsen the hue. On the other hand, if too little photopolymerization initiator is added, the polymerizable composition may not polymerize sufficiently.

[0114] <Thermal Polymerization Initiator> As the thermal polymerization initiator assisting in the polymerization of the polymerizable composition of the present invention, any known thermal free radical polymerization initiator may be used. Examples include organic peroxides and azo compounds. Among these, organic peroxides are preferred from the viewpoint that they are less likely to generate bubbles in the polymer obtained during the polymerization reaction.

[0115] Specific examples of organic peroxides include: peroxides such as methyl ethyl ketone peroxide; peroxy ketals such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydrogen peroxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; and diisopropylphenyl hydroperoxide. Dialkyl peroxides such as dibutyl peroxide and dibutyl peroxide; dibutyl peroxide such as dilauryl peroxide and dibenzoyl peroxide; dicarbonates such as di(4-tert-butylcyclohexyl) peroxide and di(2-ethylhexyl) peroxide; and peroxide esters such as tert-butyl peroxide, tert-hexyl isopropyl monocarbonate, tert-butyl peroxide, and 1,1,3,3-tetramethylbutyl-2-ethylhexanoate.

[0116] Specific examples of azo compounds include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 1,1'-azobis-1-cyclohexanenitrile, dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanopentanoic acid, and 2,2'-azobis-(2-amidinylpropane) dihydrochloride.

[0117] The thermal polymerization initiators can be used alone or in combination or ratio of two or more.

[0118] Regarding the content of the thermal polymerization initiator in the polymerizable composition of the present invention, when the total amount of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass, it is generally 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more. Its upper limit is generally 10 parts by mass or less, preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less. If there is too much thermal polymerization initiator, polymerization may proceed rapidly, which may not only impair the optical uniformity of the obtained polymer but also cause a deterioration in color. On the other hand, if there is too little thermal polymerization initiator, thermal polymerization may not proceed sufficiently.

[0119] When using both photopolymerization initiators and thermal polymerization initiators, the mass ratio is usually "100:1" to "1:100" ("photopolymerization initiator: thermal polymerization initiator", the same applies hereinafter in this paragraph), preferably "10:1" to "1:10". If there is too little thermal polymerization initiator, there will be insufficient polymerization; if there is too much thermal polymerization initiator, there is a risk of coloring.

[0120] 2-1-2. Redox polymerization initiators Redox polymerization initiators are free radical initiators that utilize the combination of peroxides and reducing agents and the redox reaction. They can generate free radicals even at low temperatures and are commonly used in emulsion polymerization, etc.

[0121] Specific examples of redox polymerization initiators include: benzoyl peroxide as a peroxide and aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as reducing agents; hydrogen peroxide as a peroxide and metal soaps as reducing agents; and hydrogen peroxide as a peroxide and thiourea as a reducing agent. Regarding water-soluble redox polymerization initiators, peroxides such as persulfates, hydrogen peroxide, and hydroperoxides are used in combination with water-soluble inorganic reducing agents (Fe2+ or NaHSO3, etc.) or organic reducing agents (alcohols, polyamines, etc.).

[0122] The suitable range of the content of redox polymerization initiator in the polymeric composition of the present invention is the same as that of thermal polymerization initiator.

[0123] 2-1-3. Anionic polymerization initiators used in the polymerizable compositions of the present invention include, for example, alkali metals, n-butyllithium, sodium amine, sodium naphthalene, Grignard reagents, lithium alkoxides, and alkali metal carbonyl benzophenone. Any one of these can be used alone, or two or more can be used in any combination and ratio.

[0124] 2-1-4. Cationic polymerization initiators used in the polymerizable compositions of the present invention include, for example: Bristol acids such as perchloric acid, sulfuric acid, and trichloroacetic acid; Lewis acids such as boron trifluoride, aluminum trichloride, aluminum tribromide, and tin tetrachloride; and iodine and trichlorotriphenylmethane. Any one of these can be used alone, or two or more can be used in any combination and ratio.

[0125] Regarding the amount of anionic polymerization initiator or cationic polymerization agent in the polymerizable composition of the present invention, relative to 100 parts by mass of all compounds capable of anionic or cationic polymerization in the polymerizable composition, it is generally 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more. Its upper limit is generally 5 parts by mass or less, preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. If the anionic or cationic polymerization initiator is less than 0.001 parts by mass, a sufficient reaction will not occur; if more than 5 parts by mass are prepared, it will be difficult to balance the applicable time and polymerization rate.

[0126] 2-1-5. Photocationic Polymerization Initiator The photocationic polymerization initiator of this invention is an initiator that generates cationic species by means of light. There are no particular limitations on the photocationic polymerization initiator; it is sufficient to be a compound that generates cationic species by light irradiation. Onionium salts are commonly known. Examples of onionium salts include: diazonium salts of Lewis acids, monium salts of Lewis acids, and strontium salts of Lewis acids. Specifically, examples include: phenyldiazonium salt of boron tetrafluoride, diphenyliodide of phosphorus hexafluoride, diphenyliodide of antimony hexafluoride, tri-4-methylphenylstrontium salt of arsenic hexafluoride, and tri-4-methylphenylstrontium salt of antimony tetrafluoride. Aromatic strontium salts are preferred.

[0127] Specific examples of photocationic polymerization initiators include: S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)distrontium bis(hexafluorophosphate), diphenyl-4-phenylthiophenyl strontium hexafluorophosphate, diphenyl-4-phenylthiophenyl strontium hexafluoroantimonate, etc. Examples include: trade name: UVI-6992 manufactured by Dow Chemical, trade name: CPI-100P manufactured by SAN-APRO, trade name: CPI-101A manufactured by SAN-APRO, trade name: CPI-200K manufactured by SAN-APRO, trade name: Omnicat 270 manufactured by IGM Resins, etc.

[0128] Any one of these photocationic polymerization initiators can be used alone, or two or more can be used together in any combination and ratio.

[0129] Regarding the amount of photocationic polymerization initiator in the polymerizable composition of the present invention, it is preferably 0.02 parts by mass to 20 parts by mass, and more preferably 0.1 parts by mass to 10 parts by mass, relative to a total of 100 parts by mass of all photocationically polymerizable compounds in the polymerizable composition. If the photocationic polymerization initiator is less than 0.02 parts by mass, a sufficient reaction will not occur; if it is prepared to exceed 20 parts by mass, it will be difficult to balance the applicable time and polymerization rate.

[0130] The above-mentioned cationic polymerization initiator may also be used in conjunction with the photocationic polymerization initiator. In this case, the cationic polymerization initiator is typically used in the range of 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, relative to 100 parts by mass of the cationic polymerizable compound in the polymerizable composition. If the amount of cationic polymerization initiator used is too small, the polymerization rate may be slowed down; on the other hand, if the amount of cationic polymerization initiator used is too large, the physical properties of the obtained polymer may be reduced.

[0131] Furthermore, a photocationic polymerization sensitizer may also be used concurrently with the photocationic polymerization initiator. A photocationic polymerization sensitizer is a formulation that efficiently transfers the energy of the irradiation light to the photocationic polymerization initiator when the irradiation wavelength of the light source used in photocationic polymerization does not match the absorption wavelength of the photocationic polymerization initiator. Known examples include phenolic compounds such as methoxyphenol (Japanese Patent Application Publication No. 5-230189), 9-oxosulfur compounds (Japanese Patent Application Publication No. 2000-204284), and dialkoxyanthracene compounds (Japanese Patent Application Publication No. 2000-119306), etc.

[0132] The photocationic polymerization sensitizer is used in a range of 0.2 to 5 parts by mass, preferably 0.5 to 1 part by mass, relative to 1 part by mass of the photocationic polymerization initiator. If the photocationic polymerization sensitizer is too small, the sensitizing effect may not be easily observed. On the other hand, if the photocationic polymerization sensitizer is too large, the physical properties of the polymer may be reduced.

[0133] 2-2. Regarding the polymeric compound contained in the polymeric composition of the present invention, it may individually include any one of the compounds of the present invention represented by formula (1), or may include two or more in any combination and ratio.

[0134] The polymeric composition of the present invention may also contain other polymeric compounds besides those of the present invention.

[0135] Regarding the content of the compound of the present invention in the polymeric composition of the present invention, it is 1% by mass or more and 99% by mass or less, as a ratio relative to the total solid content of the polymeric composition of the present invention, preferably 5% by mass or more and 95% by mass or less. If the content of the compound of the present invention is less than 1% by mass, there is a tendency for the compound of the present invention to not exert its full effect. On the other hand, if the content of the compound of the present invention exceeds 99% by mass, there is a tendency for the hardening properties to decrease.

[0136] Examples of other polymerizable compounds include cationic polymerizable monomers, anionic polymerizable monomers, and free radical polymerizable monomers. Any one of these polymerizable compounds can be used alone, or two or more can be used in any combination and ratio. Furthermore, polymerizable compounds having two or more polymerizable functional groups in one molecule (sometimes called multifunctional monomers) can also be used. When using multifunctional monomers, the formation of a cross-linked structure within the polymer can improve thermal stability, weather resistance, and solvent resistance.

[0137] When the polymeric composition of the present invention contains polymeric compounds other than those of the present invention, the content of such polymeric compounds, as a ratio to the total solid content of the polymeric composition of the present invention, is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 5% by mass or less. If the content of other polymeric compounds is less than 0.1% by mass, there is a tendency that the effect of the properties imparted by the addition of other polymeric compounds will not be fully realized. On the other hand, if the content of other polymeric compounds exceeds 5% by mass, there is a tendency that problems such as impaired optical properties or strength may easily occur.

[0138] <Catonic Polymerizable Monomer> Examples of cationic polymerizable monomers include: compounds having an ethylene oxide ring, styrene and its derivatives, vinylnaphthalene and its derivatives, vinyl ethers, N-ethylene compounds, and compounds having an oxetane ring. Preferably, compounds having at least an oxetane ring are used, and more preferably, compounds having both an oxetane ring and an ethylene oxide ring are used in combination.

[0139] Examples of compounds containing ethylene oxide rings include prepolymers containing two or more ethylene oxide rings within one molecule. Examples of such prepolymers include: alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxides, and epoxidized polybutadienes, etc.

[0140] Examples of styrene and its derivatives include: styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, divinylbenzene, etc.

[0141] Examples of vinylnaphthalene and its derivatives include: 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, etc.

[0142] Examples of vinyl ethers include: isobutyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether, etc.

[0143] Examples of N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-vinylphenanthrene, etc.

[0144] Examples of compounds having an oxetane ring include various known oxetane compounds described in Japanese Patent Application Publication No. 2001-220526 and Japanese Patent Application Publication No. 2001-310937.

[0145] Any one of these cationic polymerizable monomers may be used alone, or two or more may be used together in any combination and ratio.

[0146] <Anionic polymerizable monomer> Examples of anionic polymerizable monomers include: hydrocarbon monomers, polar monomers, etc.

[0147] Examples of hydrocarbon monomers include: styrene, α-methylstyrene, butadiene, isoprene, vinylpyridine, vinylanthracene, and their derivatives.

[0148] Examples of polar monomers include: methacrylates (e.g., methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc.); acrylates (e.g., methyl acrylate, ethyl acrylate, etc.); vinyl ketones (e.g., methyl vinyl ketone, isopropyl vinyl ketone, cyclohexyl vinyl ketone, phenyl vinyl ketone, etc.); isopropenyl ketones (e.g., methyl isopropenyl ketone, phenyl isopropenyl ketone, etc.); and other polar monomers (e.g., acrylonitrile, acrylamide, nitrosylethylene, methylene malonate, cyanoacrylate, dicyandiamide, etc.).

[0149] Any one of these anionic polymerizable monomers may be used alone, or two or more may be used together in any combination and ratio.

[0150] <Free Radical Polymerizable Monomer> A compound having one or more vinyl unsaturated double bonds in one molecule. Examples include: (meth)acrylates, (meth)acrylamides, vinyl esters, styrene, etc.

[0151] Examples of (meth)acrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate (n- or iso)acrylate, butyl methacrylate (n-, iso, second or third), pentyl methacrylate, adamantyl methacrylate, ethyl chloromethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, benzyl methacrylate, methoxybenzyl methacrylate, and benzyl chloromethacrylate. Ester, Hydroxybenzyl (meth)acrylate, Hydroxyphenylethyl (meth)acrylate, Dihydroxyphenylethyl (meth)acrylate, Methyl furan (meth)acrylate, Tetrahydrofuran (meth)acrylate, Phenyl (meth)acrylate, Hydroxyphenyl (meth)acrylate, Chlorophenyl (meth)acrylate, Aminosulfonylphenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-(hydroxyphenylcarbonyl)ethyl (meth)acrylate, Phenolic EO-modified (meth)acrylate, Phenylphenol EO-modified (meth)acrylate, p-isopropylphenylphenol EO-modified (meth)acrylate, Nonylphenol EO-modified (meth)acrylate, N-Acryloxyethylhexahydrophthalimide, Bisphenol F EO-modified diacrylates, bisphenol A EO-modified diacrylates, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentyl acrylate, tricyclodecane dimethylolpropane di(meth)acrylate, bisphenoxyethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Here, "EO" refers to "ethylene oxide".

[0152] Examples of (meth)acrylamides include: (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-butyl (meth)acrylamide, N-benzyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-tolyl (meth)acrylamide Acrylamide, N-(hydroxyphenyl)(methyl)acrylamide, N-(aminesulfonylphenyl)(methyl)acrylamide, N-(phenylsulfonyl)(methyl)acrylamide, N-(tolylsulfonyl)(methyl)acrylamide, N,N-dimethyl(methyl)acrylamide, N-methyl-N-phenyl(methyl)acrylamide, N-hydroxyethyl-N-methyl(methyl)acrylamide, etc.

[0153] Examples of vinyl esters include: vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, tert-butyl vinyl benzoate, chlorovinyl benzoate, 4-ethoxyvinyl benzoate, 4-ethylvinyl benzoate, 4-methylvinyl benzoate, 3-methylvinyl benzoate, 2-methylvinyl benzoate, 4-phenylvinyl benzoate, and vinyl tert-valerate.

[0154] Examples of styrene products include: styrene, p-acetyrene, p-benzoylstyrene, 2-butoxymethylstyrene, 4-butylstyrene, 4-dibutylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, dichlorostyrene, 2,4-diisopropylstyrene, dimethylstyrene, p-ethoxystyrene, 2-ethylstyrene, 2-methoxystyrene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, p-methylstyrene, p-phenoxystyrene, p-phenylstyrene, divinylbenzene, etc.

[0155] Any one of these free radical polymerizable monomers may be used alone, or two or more may be used together in any combination and ratio.

[0156] The cationic polymerizable monomers, anionic polymerizable monomers, and free radical polymerizable monomers exemplified above can all be used, and two or more can be used in combination. When used in holographic recording media, as other polymerizable compounds used in combination with the compounds of the present invention represented by formula (1), free radical polymerizable monomers are preferred because they are less likely to hinder the reaction that forms the resin matrix.

[0157] 2-3 Other Additives In the polymeric composition of the present invention, other components may be formulated within a range that does not impair the effects of the present invention.

[0158] Other components may include, for example: solvents, antioxidants, plasticizers, ultraviolet absorbers, sensitizers, chain transfer agents, defoamers, polymerization inhibitors, any fillers containing organic or inorganic substances, dispersants, pigments, phosphors and other wavelength conversion materials and various additives.

[0159] The polymeric composition of the present invention may also contain a solvent to adjust the viscosity.

[0160] Specific examples of solvents, depending on the physical properties of the polymerizable composition, include, for example: alcohols such as ethanol, propanol, isopropanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as hexane, pentane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; chain ethers such as dimethyl ether and diethyl ether; cyclic ethers such as dimethyl ether and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate; acetone, methyl ethyl ketone, and methyl isopropanol. Ketones such as butyl ketone and cyclohexanone; cellosols such as methyl cellosol, ethyl cellosol, and butyl cellosol; carbitols such as methyl carbitol, ethyl carbitol, and butyl carbitol; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; N,N-dimethylformamide, N,N-dimethylacetamide, etc.; acetamides such as dimethyl acetamide; nitriles such as acetonitrile and benzonitrile; and organic solvents such as N-methylpyrrolidone.

[0161] These solvents can be used alone or in mixtures. Water may also be used depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.). There are no particular limitations on the amount of solvent (or dispersion medium) used; it is sufficient to adjust and use it in a manner that produces a polymerizable composition of suitable viscosity, depending on the polymerization method, processing method, and intended use.

[0162] In this invention, in order to improve the heat resistance and weather resistance of the obtained polymer, it is preferable to formulate an antioxidant or light stabilizer as an additive into the polymeric composition.

[0163] Specific examples of antioxidants include: 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.; and triphenyl phosphite, triisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, tetra(C Phosphorus-based antioxidants such as (12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, tri(nonylphenyl) phosphite, tri(tetrazyl) phosphite, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxophosphataoctacyclobenzene, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di-octadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and tri(2,4-di-tert-butylphenyl) phosphite. These can be used alone or in combination of two or more.

[0164] Preferably, the antioxidant is a combination of a phenolic antioxidant and a phosphorus antioxidant. Examples of a preferred combination of a phenolic antioxidant and a phosphorus antioxidant include: a combination of at least one of tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane and octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate as a phenolic antioxidant, and tris(2,4-di-tert-butylphenyl) phosphite as a phosphorus antioxidant.

[0165] Regarding the amount of antioxidant in the polymeric composition of the present invention, based on the consideration of making the heat resistance and yellowing resistance of the obtained polymer good, it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the polymeric composition.

[0166] Hindered amine light stabilizers (HALS) are suitable as light stabilizers. Specific examples of HALS include: 2,2,6,6-tetramethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Adekastab LA-68 (manufactured by ADEKA Corporation), Adekastab LA-63P (manufactured by ADEKA Corporation), butane-1,2,3,4-tetracarboxylate tetra(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,2,3,4-butanetetracarboxylate tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TINUVIN 292, TINUVIN 5100 (all manufactured by BASF), etc. These can be used alone or in combination of two or more.

[0167] Based on the consideration of making the obtained polymer have good heat resistance to yellowing or weather resistance, the amount of light stabilizer in the polymeric composition of the present invention is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the polymeric composition, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass.

[0168] Antioxidants or light stabilizers may be used alone or in combination of two or more.

[0169] 2-4 Method for manufacturing polymerizable compositions The polymerizable compositions of the present invention can be manufactured by mixing the components, or by pre-mixing the components other than the polymerization initiator and adding the polymerization initiator just before the polymerization reaction.

[0170] 3. Polymerization method of the polymerizable composition of the present invention The polymerization method of the polymerizable composition of the present invention is not particularly limited, including methods of polymerization by irradiation of active energy lines and methods of polymerization by heating.

[0171] 3-1. Polymerization Initiation Method (Active Energy Line) When performing photoradical polymerization of the polymerizable composition of the present invention, an active energy line is irradiated. Preferably, the active energy line used is an electron beam or light in the wavelength range from ultraviolet to infrared. As a light source, for example, if the active energy line is ultraviolet, an ultra-high pressure mercury light source or a metal halide light source can be used; if it is visible light, a metal halide light source or a halogen light source can be used; if it is infrared, a halogen light source can be used. In addition, lasers, LEDs, and other light sources can also be used.

[0172] The irradiation dose of the active energy line is appropriately set according to the type of light source, the film thickness, etc., preferably to achieve a reaction rate of 80% or more, more preferably 90% or more, of the total amount of polymerizable functional groups of the compound of the present invention and other polymeric compounds represented by formula (1). The reaction rate is calculated based on the change in the intensity of the absorption peak of the polymerizable functional groups before and after the reaction, according to the infrared absorption spectrum. After polymerization by irradiation with the active energy line, heat treatment or annealing treatment may be performed as needed to further the polymerization. The heating temperature is preferably in the range of 80 to 200°C. The heating time is preferably in the range of 10 to 60 minutes.

[0173] 3-2. Polymerization Initiation Method (Heating) When heat treatment is performed to polymerize the polymerizable composition of the present invention, the heating temperature is preferably in the range of 80 to 200°C, and more preferably in the range of 100 to 150°C. If the heating temperature is below 80°C, the heating time needs to be extended, which is often not economical. If the heating temperature is above 200°C, energy costs are incurred, and heating and cooling times are also consumed, which is often not economical.

[0174] 4. Polymers Hereinafter, polymers of the present invention formed by polymerizing the polymeric composition of the present invention will be described.

[0175] 4-1. Refractive Index Generally, the overall density increases due to polymerization, therefore the refractive index of a polymer is often higher than that of the precursor compound (called a monomer). By using monomers with high refractive indices to allow the polymerization reaction to proceed sufficiently, the refractive index of the obtained polymer can be increased. Therefore, it is considered important to increase the refractive index of the polymer through the molecular structure design of the monomer. Regarding refractive index, a larger value is observed when evaluated with short-wavelength illumination light. However, samples that show a relatively large refractive index at short wavelengths also show a relatively large refractive index at long wavelengths; this relationship is not reversed. Therefore, by evaluating and comparing the refractive index at a fixed wavelength, the magnitude of the intrinsic refractive index of the material can be compared. In this invention, the value of the illumination wavelength of 587 nm is used as a reference.

[0176] The refractive index of the polymer of the present invention is preferably 1.55 or higher, more preferably 1.60 or higher, even more preferably 1.63 or higher, and most preferably 1.65 or higher. There is no particular upper limit to the refractive index of the polymer of the present invention, and it is generally 2.0 or lower. When using the polymer of the present invention as an optical material for lenses, etc., if the refractive index is less than 1.55, the central portion of the optical lens, etc., may become thicker, which impairs the lightweight properties characteristic of plastics, and is therefore undesirable. Furthermore, in the development of precision optical components such as lenses, it is also important to achieve suitable optical properties for the component by combining optical materials having multiple refractive indices. Based on this viewpoint, polymers with a refractive index exceeding 1.63 are particularly useful materials suitable for optical components.

[0177] When the polymer of the present invention is used as the recording layer material of a holographic recording medium, the refractive index of the polymer of the present invention is generally in the range of 1.65 or higher and 1.78 or lower, preferably 1.77 or lower. If the refractive index is less than 1.65, the diffraction efficiency is low and the multiplicity is insufficient. Furthermore, if the refractive index is greater than 1.78, the difference between the refractive index and the matrix resin becomes too large, resulting in increased scattering, thus reducing transmittance, and requiring more energy during recording or playback.

[0178] 4-2. Glass Transfer Temperature The glass transfer temperature of the polymer of the present invention is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 110°C or higher, particularly preferably 120°C or higher, and preferably 250°C or lower, even more preferably 220°C or lower, and even more preferably 200°C or lower. If it is below this range, the optical properties may deviate from the design values ​​under the operating environment, and the required heat resistance may not be met. Furthermore, if it is above this range, the processability of the polymer may decrease, making it impossible to obtain a molded article with a good appearance or high dimensional accuracy. In addition, the polymer may become brittle and its mechanical strength may decrease, thereby reducing the operability of the molded article.

[0179] 5. Optical materials and optical components The compounds, polymeric compositions and polymers of the present invention have properties such as high refractive index, easy processability and low shrinkage, and are therefore applicable to various optical materials and optical components.

[0180] Examples of optical materials include: optical coatings, hard coatings, adhesives for optical components, resins for optical fibers, and acrylic resin modifiers. Examples of optical components include: lenses, filters, diffraction gratings, prisms, light guides, cover glass for display devices, photosensors, optical switches, LEDs, light-emitting elements, optical waveguides, optical splitters, optical fiber adhesives, substrates for display elements, substrates for color filters, substrates for touch panels, polarizing plates, display backlight devices, light guide plates, anti-reflective films, viewing angle expanding films, optical recording, optical shaping, and optical embossing. Furthermore, it can also be used as a layer for these components. Examples include display protective films.

[0181] In particular, considering the high refractive index characteristics of the polymer of the present invention, it can be preferably applied to plastic lenses. Examples of lenses include: imaging lenses, lens elements, beam focusing lenses, and light diffusing lenses for cameras (vehicle cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.). For lenses using the polymer of the present invention, physical or chemical treatments such as surface grinding, antistatic treatment, hard coating treatment, anti-reflective coating treatment, and dyeing treatment can be performed as needed to improve them, such as by increasing anti-reflection properties, imparting high hardness, improving wear resistance, improving chemical resistance, imparting anti-fog properties, or imparting a fashionable appearance.

[0182] 6. Holographic Recording Media The polymeric composition of the present invention is suitable for use in the recording layer of a holographic recording media. Preferably, the polymeric composition of the present invention is a photoreactive composition comprising, in addition to the compounds of the present invention, a matrix resin, a photopolymerization initiator, a free radical scavenger, and other additives. Details regarding its use as a material suitable for holographic recording media will be described below.

[0183] 6-1. Regarding the matrix resin, the polymerizable composition of the present invention preferably includes a matrix resin. In particular, the matrix resin constituting the recording layer of the holographic recording medium is an organic material that does not undergo chemical or physical changes due to light exposure, and mainly comprises a polymer of organic compounds.

[0184] Since the matrix resin, together with the aforementioned polymerizable compound or the photopolymerization initiator described below, constitutes the polymerizable composition of the present invention, excellent compatibility with the polymerizable compound or photopolymerization initiator is strongly required. If the compatibility of the matrix resin with the other components described above is low, an interface will form between the materials, and light will be refracted or reflected at the interface, resulting in light leakage to unwanted parts. Therefore, interference fringes may be distorted or cut and recorded in inappropriate parts, thereby causing information degradation. Regarding the compatibility of the matrix resin with the other components described above, for example, as described in Japanese Patent No. 3737306, the sample is evaluated based on the intensity of scattered light obtained by setting a detector in a direction different from the transmitted light.

[0185] The matrix resin of the polymeric composition of the present invention includes a plurality of materials that can be dissolved in a solvent in the polymeric composition, and may also be a resin formed by three-dimensional cross-linking of such materials after being formed to the use state, such as thermoplastic resin, thermosetting resin and photosetting resin described below.

[0186] The three-dimensionally cross-linked resin is solvent-insoluble and is a reaction-cured product of a polymeric compound that is liquid at room temperature and a compound that is reactive with the polymeric compound. The three-dimensionally cross-linked resin acts as a physical barrier, thus suppressing volume changes during recording. That is, in the recording layer after recording, bright areas tend to expand while dark areas shrink, resulting in unevenness on the surface of the holographic recording medium. To suppress this volume change, the recording layer preferably uses a polymeric composition containing a three-dimensionally cross-linked resin matrix. From the viewpoint of adhesion to the support, a thermosetting resin is preferred as the matrix resin. Hereinafter, resin materials that can be used as matrix resins will be described in detail.

[0187] 6-1-1. Examples of specific thermoplastic resins include: chlorinated polyethylene, polymethyl methacrylate (PMMA), copolymers of methyl methacrylate and other alkyl acrylates, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate resin (PVAC), polyvinyl alcohol, polyvinyl formaldehyde, polyvinylpyrrolidone, cellulose resins such as ethyl cellulose or nitrocellulose, polystyrene resin, polycarbonate resin, etc. One of these may be used alone, or two or more may be used in combination.

[0188] As a solvent for these thermoplastic resins, there are no particular limitations as long as it is used to dissolve them, and examples include: ketones such as acetone and methyl ethyl ketone; esters such as butyl acetate and propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ethers such as tetrahydrofuran and 1,2-dimethoxyethane; and amides such as N,N-dimethylacetamide and N-methylpyrrolidone. Only one of these solvents may be used, or two or more may be mixed.

[0189] 6-1-2. When thermosetting resins are used as the matrix resin, the curing temperature varies depending on the type of crosslinking agent or catalyst. Representative examples of functional group combinations that cure at room temperature include: epoxy resin and amine, epoxy resin and thiol, and isocyanate and amine. Representative examples of catalysts include: epoxy resin and phenol, epoxy resin and acid anhydride, and isocyanate and polyol.

[0190] The former reacts immediately upon mixing, making it simpler, but it is difficult to adjust due to time constraints when involved in processes such as the molding of holographic recording media. On the other hand, the latter allows for flexible selection of curing temperature or time by appropriately choosing the type and amount of catalyst used, making it more suitable for curing processes such as those involving the molding of holographic recording media. Various resin raw materials, ranging from low to high molecular weight, are commercially available, allowing for the maintenance and selection of compatibility with polymerizable reactive compounds or photoinitiators, as well as adhesion to the substrate. The following describes each raw material, but each raw material can be used individually or in combination of two or more.

[0191] <Epoxide> Examples of epoxides include: polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxides with cyclic aliphatic groups having 4 to 7 members, such as methyl 3,4-epoxycyclohexylcarboxylic acid and methyl 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylic acid ester; bisphenol A type epoxides; hydrogenated bisphenol A type epoxides; bisphenol F type epoxides; and phenol or cresol phenolic varnish type epoxides.

[0192] Epoxides are preferably those having two or more epoxy groups per molecule, and there is no particular limitation on the type. If the number of epoxy groups is low, the required hardness as a matrix may not be achieved. There is no particular limit to the upper limit of the number of epoxy groups per molecule, but it is generally preferred to be 8 or less, especially 4 or less. If the number of epoxy groups is too high, it may take longer to consume the epoxy groups, resulting in an excessively time-consuming matrix resin.

[0193] <Amine> As an amine, those containing primary or secondary amino groups can be used. Examples of such amines include: aliphatic polyamines such as ethylenediamine, diethylenetriamine or its derivatives; alicyclic polyamines such as isophorone diamine, menthane diamine, N-aminoethylpiperazine or its derivatives; aromatic polyamines such as m-phenylenediamine, diaminodiphenylmethane or its derivatives; polyamides such as condensates of dicarboxylic acids such as dimer acids with the above-mentioned polyamines; imidazole compounds such as 2-methylimidazole or its derivatives; and dicyandiamide, diazide adipic acid, etc., other than these.

[0194] <Thiols> Examples of thiols include: 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-phenylenediol, 1,3-phenylenediol, 1,4-phenylenediol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, etc.; and polythiols such as polysulfide rubber (manufactured by TORAY FINE CHEMICALS) and jER Cure QX40 (manufactured by Mitsubishi Chemical). Among these, commercially available fast-curing polythiols such as jER Cure QX40 are suitable.

[0195] <Phenol> Examples of phenols include: bisphenol A, phenolic resins, and soluble phenolic resins.

[0196] <Acid Anhydride> Examples of acid anhydrides include: phthalic anhydride, tetrahydrophthalic anhydride or its derivatives, which are monofunctional acid anhydrides; and pyromellitic dianhydride, benzophenone tetracarboxylic anhydride or its derivatives, which are difunctional acid anhydrides.

[0197] <Amounts of Amines, Thiols, Phenols, and Acid Anhydrides> The amounts of amines, thiols, phenols, and acid anhydrides used, in proportion to the molar number of epoxy groups, are preferably in the range of 0.1 equivalents or more, especially 0.7 equivalents or more, and usually 2.0 equivalents or less, especially 1.5 equivalents or less. If the amounts of amines, thiols, phenols, and acid anhydrides used are too small or too large, there may be a greater number of unreacted functional groups, which may compromise storage stability.

[0198] <Polymerization Initiator for Thermosetting Resins> As a catalyst for curing thermosetting resins, anionic polymerization initiators and cationic polymerization initiators can be used depending on the curing temperature or curing time.

[0199] Anionic polymerization initiators are those that generate anions by irradiation with heat or active energy lines. Examples include amines. Examples of amines include: dimethylbenzylamine, dimethylaminomethylphenol, 1,8-diazabicyclo[5.4.0]undecene-7 and other amine-containing compounds, and their derivatives; imidazole compounds such as imidazole, 2-methylimidazolium, 2-ethyl-4-methylimidazolium and their derivatives. One or more of these may be used depending on the curing temperature or curing time.

[0200] Cationic polymerization initiators are those that generate cations through heat or active energy line irradiation. Examples include aromatic onium salts. Specific examples include compounds containing anionic components such as SbF6-, BF4-, AsF6-, PF6-, CF3SO3-, and B(C6F5)4-, and aromatic cationic components containing atoms such as iodine, sulfur, nitrogen, and phosphorus. Among these, diaryl strontium salts and triaryl strontium salts are preferred. One or more of these can be used depending on the curing temperature or curing time.

[0201] The amount of polymerization initiator used in these thermosetting resins is preferably in the range of 0.001% by mass or more, especially 0.01% by mass or more, and usually 50% by mass or less, especially 10% by mass or less, relative to the matrix resin. If the amount of polymerization initiator used in these thermosetting resins is too small, the concentration of the polymerization initiator for the thermosetting resin is too low, and therefore the polymerization reaction sometimes takes too long. On the other hand, if the amount of polymerization initiator used in the thermosetting resin is too large, sometimes the continuous ring-opening reaction that is the polymerization reaction will no longer occur.

[0202] <Isocyanate> As an isocyanate, it is preferable to have two or more isocyanate groups per molecule, and there is no particular limitation on the type. If the number of isocyanate groups per molecule is small, the hardness required as a matrix resin may not be obtained. There is no particular limit to the upper limit of the number of isocyanate groups per molecule, but it is generally preferred to be 8 or less, especially 4 or less. If the number of isocyanate groups per molecule is too large, it may take a long time to consume the isocyanate groups, thus making the formation of the matrix resin too time-consuming. There is no particular limit to the upper limit of the number of isocyanate groups per molecule, but it is generally around 20 or less.

[0203] Examples of isocyanates include: aliphatic isocyanates such as hexamethylene diisocyanate, methyl lysine diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and 4,4'-methylene bis(cyclohexyl isocyanate); aromatic isocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenyl dimethyl diisocyanate, and naphthalene-1,5'-diisocyanate; and polymers thereof, especially 3- to 7-mers.

[0204] In addition, examples include: reactants of water, trimethylolethane, trimethylolpropane, and other polyols with the above-mentioned isocyanates, polymers of hexamethylene diisocyanate, or their derivatives. The molecular weight of the isocyanate, in terms of number average molecular weight, is preferably 100 to 50,000, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is too small, the crosslinking density increases, thus the hardness of the matrix resin becomes too high, which may lead to a decrease in recording speed. Conversely, if the number average molecular weight is too large, the compatibility with other components decreases or the crosslinking density decreases, thus the hardness of the matrix resin becomes too low, and sometimes the recorded content may disappear.

[0205] <Polyol> Examples of polyols include: polypropylene polyol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, etc.

[0206] (Polypropylene Polyol) Polypropylene polyol is obtained by reacting propylene oxide with a glycol or polyol. Examples of glycols or polyols include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decamethylethylene glycol, polyethylene glycol, and polytetramethylene glycol. Commercially available polypropylene polyols include: SANNIX GP-400 and GP-1000 (both manufactured by Sanyo Chemical Co., Ltd., trade names), and ADEKA polyether G400, G700, and G1500 (all manufactured by ADEKA Corporation, trade names), etc.

[0207] (Polycaprolactone polyol) Polycaprolactone polyol is obtained by reacting a lactone with a diol or polyol. Examples of lactones include α-caprolactone, β-caprolactone, γ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, etc.

[0208] As a diol or polyol, examples include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decamethyldiol, polyethylene glycol, polytetramethylenediol, etc.

[0209] Commercially available polycaprolactone polyols obtained from the reaction of ε-caprolactone include: PLACEL 205, PLACEL 205H, PLACEL 205U, PLACEL 205UT, PLACEL 210, PLACEL 210N, PLACEL 210CP, PLACEL 220, PLACEL 230, PLACEL 230N, PLACEL 240, PLACEL 220EB, PLACEL 220EC, PLACEL 303, PLACEL 305, PLACEL 308, PLACEL 309, PLACEL 312, PLACEL 320, PLACEL 401, PLACEL L205AL, PLACEL L212AL, PLACEL L220AL, PLACEL L320AL, PLACEL T2103, PLACEL T2205, PLACEL P3403, PLACEL 410 (all manufactured by Daicel Inc., trade names), etc.

[0210] (Polyester Polyol) Examples of polyester polyols include those obtained by polycondensation of dicarboxylic acid or such anhydrides with a polyol.

[0211] As dicarboxylic acids, examples include: succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, etc.

[0212] Examples of polyols include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decamethyldiol, polyethylene glycol, polytetramethylenediol, etc.

[0213] Examples of polyester polyols include: polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. Commercially available polyester polyols include: Adeka New Ace F series, Adeka New Ace Y series, Adeka New Ace NS series (manufactured by ADEKA Corporation, trade name), KURARAY POLYOL N-2010, P-4011, and P-1020 (all manufactured by Kuraray Corporation, trade name), etc.

[0214] (Polycarbonate polyols) Examples of polycarbonate polyols include those obtained by the alcohol removal condensation reaction of diols with dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, etc.), those obtained by the phenol removal condensation reaction of diols with diphenyl carbonates, and those obtained by the alcohol removal condensation reaction of diols with carbonates (e.g., ethylene carbonate, diethyl carbonate, etc.).

[0215] As diols, examples include: aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and neopentanediol, or alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanediethanol.

[0216] Examples of polycarbonate polyols include: poly(hexamethylene carbonate) polyol obtained by condensation reaction of 1,6-hexanediol and diethyl carbonate, poly(pentanediol carbonate) obtained by condensation reaction of pentanediol and diethyl carbonate, and poly(butylene carbonate) obtained by condensation reaction of 1,4-butanediol and diethyl carbonate.

[0217] Commercially available polycarbonate polyols include: PLACEL CD CD205, PLACEL CD CD210, PLACEL CD CD220 (all manufactured by Daicel Co., Ltd., trade name), DURANOL T5651, DURANOL T5652, DURANOL T5650J (all manufactured by Asahi Kasei Co., Ltd., trade name), etc.

[0218] (Molecular weight of polyols) The molecular weight of the polyols described above is based on the number average molecular weight, preferably between 100 and 50,000, more preferably between 150 and 10,000, and even more preferably between 150 and 5,000. If the number average molecular weight is too small, the crosslinking density increases, thus the hardness of the matrix resin becomes too high, which may lead to a decrease in recording speed. Conversely, if the number average molecular weight is too large, the compatibility with other components decreases or the crosslinking density decreases, thus the hardness of the matrix resin becomes too low, and sometimes the recorded content may disappear.

[0219] <Other Components> In addition to the above-mentioned components, the matrix resin in this embodiment may also contain other components, as long as it does not violate the spirit of this invention.

[0220] As other components, examples include compounds containing hydroxyl groups such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decamethyldiol, trimethylolpropane, polyethylene glycol, and polytetramethylenediol, used for the purpose of altering the physical properties of the matrix resin.

[0221] <Carbamate Polymerization Catalyst> To promote the reaction between isocyanates and polyols, a suitable carbamate polymerization catalyst may also be included. Examples of carbamate polymerization catalysts include: bis(4-tert-butylphenyl)monazine perfluoro-1-butanesulfonic acid, bis(4-tert-butylphenyl)monazine p-toluenesulfonic acid, bis(4-tert-butylphenyl)monazine trifluoromethanesulfonic acid, (4-bromophenyl)diphenylstrontium trifluoromethanesulfonate, (4-tert-butylphenyl)diphenylstrontium trifluoromethanesulfonic acid, diphenylmonazine perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylstrontium trifluoromethanesulfonic acid, diphenyl-4-methylphenylstrontium trifluoromethanesulfonic acid, triphenylstrontium trifluoromethanesulfonic acid, bis(alkylphenyl)monazine hexafluorosulfonic acid, and other onium salts; and zinc chloride, tin chloride, ferric chloride, aluminum chloride, BF3, and other Lewisite salts. Catalysts with succinic acid as the main component; protic acids such as hydrochloric acid and phosphoric acid; amines such as trimethylamine, triethylamine, triethylenediamine, dimethylbenzylamine, and diazabicycloundecene; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-undecylimidazoleonium trimellitate; alkalis such as sodium hydroxide, potassium hydroxide, and potassium carbonate; tin catalysts such as dibutyltin laurate, dioctyltin laurate, and dibutyltin octanoate; bismuth catalysts such as tris(2-ethylhexanoate)bismuth and tribenzoxyloxybismuth; zirconium catalysts such as tetra(ethylacetate)zirconium, 1,1'-isopropylidene dichlorodicyclopentadienzocarboxylate, and tetra(2,4-pentanedione)zirconium, etc.

[0222] Among them, in order to improve storage stability, bismuth catalyst or zirconium catalyst is preferred.

[0223] As a bismuth-based catalyst, it is a catalyst containing bismuth element. There are no particular restrictions as long as it is a compound that promotes the reaction of isocyanates and polyols. Examples of bismuth-based catalysts include: tris(2-ethylhexanoic acid)bismuth, tribenzoxybismuth, triacetate, tri(dimethyldithiocarbamate)bismuth, bismuth hydroxide, bis(trichloroacetic acid)triphenylbismuth (V), tri(4-methylphenyl)syloxybismuth (V), triphenylbis(3-chlorobenzoxybismuth) (V), etc.

[0224] Among these, considering the catalytic activity, a trivalent bismuth compound is preferred, and more preferably bismuth carboxylate or a compound represented by the general formula Bi(OCOR)3 (where R is a straight-chain or branched alkyl, cycloalkyl, or substituted or unsubstituted aromatic group). Any of the above-mentioned bismuth-based catalysts can be used alone, or two or more can be used in any combination and ratio.

[0225] As a zirconium-based catalyst, it is a catalyst containing zirconium element, and there are no particular restrictions as long as it is a compound that promotes the reaction of isocyanates and polyols. Examples include: cyclopentadienyl zirconium trichloride, decamethylzirconia, 1,1'-dibutylzirconia, 1,1'-isopropylidenezirconia, tetra(2,4-pentanedione)zirconia, tetra(trifluoro-2,4-pentanedione)zirconia, tetra(hexafluoro-2,4-pentanedione)zirconia, zirconium butoxide, zirconium tributoxide, zirconium propoxide, zirconium isopropoxide, zirconium ethoxide, bis(ethylacetate)dibutoxyzirconia, zirconium tetra(ethylacetate)zirconia, zirconium oxide, barium zirconium oxide, calcium zirconium oxide, zirconium bromide, zirconium chloride, zirconium fluoride, zirconium dichloride (indenyl)zirconia, zirconium carbonate, etc.

[0226] Among these, considering compatibility with other components, it is preferable to use a compound having an organic ligand, more preferably an alkoxide, or a compound having an acetylacetate (2,4-pentanediol) structure. Any one of the above zirconium compounds may be used alone, or two or more may be used in any combination and ratio.

[0227] Bismuth-based catalysts and zirconium-based catalysts can be used separately or in combination.

[0228] The amount of urethane polymerization catalyst used, in ratio to the matrix resin, is preferably in the range of 0.0001% by mass or more, especially 0.001% by mass or more, and usually 10% by mass or less, especially 5% by mass or less. If the amount of urethane polymerization catalyst used is too small, curing may sometimes take too long. On the other hand, if the amount of urethane polymerization catalyst used is too large, the curing reaction may sometimes be difficult to control.

[0229] It can be cured at room temperature by using a urethane polymerization catalyst, but it can also be cured by increasing the temperature. The preferred temperature for this purpose is between 40°C and 90°C.

[0230] 6-1-3. When using a photocurable resin as a base resin, a photoinitiator for the base resin that matches the wavelength used is required for curing. Since curing during light irradiation can hinder molding or bonding, a curing reaction that is stable near room temperature, which is the primary operating temperature, is ideal. Therefore, catalytic curing using a photoinitiator for the base resin is an ideal choice.

[0231] Generally speaking, a matrix resin can generate either cationic or anionic active matrix from a photoinitiator when exposed to light. Therefore, it is advisable to select a matrix resin that can be cured by curing such an active matrix to produce the matrix resin.

[0232] Examples of functional groups that react with cations such as protons include epoxy groups and oxocyclobutyl groups. Specifically, examples of compounds containing epoxy groups include: polyglycidyl ether compounds of polyols such as polyethylene glycol, polypropylene glycol, tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxy compounds with cyclic aliphatic groups having 4 to 7 members, such as 3,4-epoxycyclohexanecarboxylic acid methyl ester and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylic acid ester; bisphenol A type epoxy compounds; hydrogenated bisphenol A type epoxy compounds; bisphenol F type epoxy compounds; and phenol or cresol phenolic varnish type epoxy compounds. Examples of compounds containing oxetane butyl groups include 2-ethyl-2-oxetane butyl ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetanebutoxy)hexane. (Furthermore, the reference to "(poly) glycol" here refers to both "ethylene glycol" and its polymer "polyethylene glycol".)

[0233] Examples of functional groups that react with anions include epoxy groups and cyclic sulfide groups. Specifically, examples of compounds containing cyclic sulfide groups include phenyl cyclic sulfides and bisphenol A dicyclic sulfide.

[0234] When photocuring the matrix resin as described above, the amount of photoinitiator used for the matrix resin, in terms of the ratio to the polymerizable compound, is preferably in the range of 0.01% by mass or more, especially 0.1% by mass or more, and usually 1% by mass or less, especially 0.5% by mass or less. If the amount of photoinitiator used for the matrix resin is too small, the curing time may sometimes be too long. On the other hand, if the amount of photoinitiator used for the matrix resin is too large, it may be difficult to control the curing reaction.

[0235] Furthermore, especially when used as a holographic recording material, since light is also irradiated during recording, it is important that the wavelength during curing differs from the wavelength during recording. The wavelength difference should be at least 10 nm, and preferably 30 nm. The selection of photoinitiators for the matrix resin can be roughly predicted based on the absorption wavelength of the initiator.

[0236] 6-2. Photopolymerization Initiator The photopolymerization initiator for the polymerization of the compounds of the present invention can be any known photoradical polymerization initiator. Examples include azo compounds, azido compounds, organic peroxides, organoborates, onium salts, imidazolium derivatives, titanocene compounds, iodides, organothiols, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, 9-oxosulfuron, anthraquinones, ketals, phosphine oxides, sulfonates, carbamate derivatives, sulfonamides, triarylethanols, and oxime esters. Among these, titanocene compounds, phosphine oxides, and oxime esters are preferred as photopolymerization initiators, considering that the polymerization reaction is induced by light in the visible light range.

[0237] 6-2-1. When using a diacene compound as a photopolymerization initiator, there is no particular limitation on the type of diacene compound. For example, it can be appropriately selected from various diacene compounds described in Japanese Patent Application Publication No. 59-152396 and Japanese Patent Application Publication No. 61-151197.

[0238] Specific examples of titanium diacene compounds include: bis(cyclopentadienyl)titanium dichloride, bisphenylbis(cyclopentadienyl)titanium, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-pentafluorobenzyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorobenzyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,6-di-fluorobenzyl-1-yl)titanium, and bis(cyclopentadienyl)bis(2,6-di-fluorobenzyl-1-yl)titanium. Di(cyclopentadienyl)bis(2,4-di-fluorophenyl-1-yl)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, di(methylcyclopentadienyl)bis(2,3,5,6-pentafluorophenyl-1-yl)titanium, di(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium, di(cyclopentadienyl)bis(2,6-difluoro-3-(pyridin-1-yl)-phenyl-1-yl)titanium, etc.

[0239] 6-2-2. Specific examples of amide phosphine oxide compounds include: monofunctional initiators with only one photodecomposition site in one molecule and difunctional initiators with two photodecomposition sites in one molecule.

[0240] Examples of monofunctional initiators include: triphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.

[0241] Examples of 2-functional initiators include: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, etc.

[0242] 6-2-3. Specific examples of oxime ester compounds include: 1-[4-(phenylthio)-2-(O-benzoyl oxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylgoxime) acetone, 4-(acetoxyimino)-5-[9-ethyl-6-(2-methylbenzyl)]-1-(O-acetylgoxime) acetone. Methyl 1-(9-ethyl-6-cyclohexyl-9H-carbazole-3-yl)-1-(O-acetylgoxime) glutarate, methyl 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetylgoxime) glutarate, methyl 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetylgoxime) glutarate, methyl 1-(O-acetylgoxime)-3-methyl-butyric acid 1-(9-ethyl-9H-carbazole-3-yl) ester, etc.

[0243] 6-2-4. Dosage of Photopolymerization Initiators The above-mentioned photopolymerization initiators can be used alone, or two or more can be used together in any combination and ratio.

[0244] The content of the photopolymerization initiator in the polymerizable composition of the present invention, based on moles per unit weight of the polymerizable composition, is preferably 0.5 μmol / g or more. More preferably 1 μmol / g or more. Furthermore, the content of the photopolymerization initiator in the polymerizable composition of the present invention, based on moles per unit weight of the polymerizable composition, is preferably 100 μmol / g or less. More preferably 50 μmol / g or less.

[0245] If the content of the photopolymerization initiator is too low, the amount of free radicals generated will be less, which may slow down the photopolymerization rate and result in a decrease in the recording sensitivity of the holographic recording medium. On the other hand, if the content of the photopolymerization initiator is too high, the free radicals generated by light irradiation may re-bond with each other or become heterogeneous, which may reduce the assistance to photopolymerization and still lead to a decrease in the recording sensitivity of the holographic recording medium. When using two or more photopolymerization initiators, it is preferable to ensure that their total amount meets the above-mentioned range.

[0246] 6-3. Free radical scavengers can also be added to holographic recording to accurately fix the interference light intensity pattern into the polymer distribution in the holographic recording medium. The free radical scavenger is preferably a combination of a functional group that scavenges free radicals and a reactive group that is covalently fixed to the matrix resin. Examples of functional groups that scavenge free radicals include stabilizing nitro radicals.

[0247] 6-3-1. Types of free radical scavengers As reactive groups that are covalently fixed to the matrix resin, examples include: hydroxyl, amino, isocyanate, and thiol groups. Examples of such free radical scavengers include: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxy radical, and 5-HO-AZADO:5-hydroxy-2-azatricyclo[3.3.1.13,7]decane N-oxy radical.

[0248] 6-3-2. Content of Free Radical Scavenger The various free radical scavengers described above can be used individually, or two or more can be used in any combination and ratio. The content of the free radical scavenger in the polymeric composition of the present invention, based on moles per unit weight of the polymeric composition, is preferably 0.5 μmol / g or more, more preferably 1 μmol / g or more. Furthermore, the content of the free radical scavenger in the polymeric composition of the present invention is preferably 100 μmol / g or less, more preferably 50 μmol / g or less.

[0249] If the content of the free radical scavenger is too low, the efficiency of scavenging free radicals will often be low, low-polymerization-degree polymers will diffuse, and there will be more components that do not contribute to the signal. On the other hand, if the content of the free radical scavenger is too high, the polymerization efficiency of the polymer will often be reduced, and signal recording will be impossible. When using two or more free radical scavengers, it is preferable to ensure that their total dosage meets the above-mentioned range.

[0250] 6-4. Other components In addition to the above-mentioned components, the polymeric composition of the present invention may also contain other components, as long as they do not violate the spirit of the present invention.

[0251] Other components may include: solvents, plasticizers, dispersants, leveling agents, defoamers, adhesion promoters, etc., used to prepare polymerizable compositions. Especially in the case of holographic recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, sensitizers, etc., used for recording reaction control, may be included. Furthermore, other additives that may be needed for property improvement may include: preservatives, stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, etc. Any one of these components may be used alone, or two or more may be used in any combination and ratio.

[0252] <Senser> In the polymerizable composition of the present invention, a compound that controls the excitation of the photopolymerization initiator may be added. Examples of such compounds include sensitizers and sensitizing aids.

[0253] As a sensitizer, any one of the various known sensitizers can be selected. Generally, colored compounds such as pigments are used as sensitizers to absorb visible and ultraviolet laser light. In the case of holographic recording media, although the choice depends on the wavelength of the laser light used for recording and the type of initiator used, specific examples of preferred sensitizers in systems using green lasers include compounds described in Japanese Patent Application Publication No. 5-241338, Japanese Patent Application Publication No. 2-69, and Japanese Patent Application Publication No. 2-55446. In the case of systems using blue lasers, examples include compounds described in Japanese Patent Application Publication No. 2000-10277 and Japanese Patent Application Publication No. 2004-198446. Any one of these sensitizers can be used alone, or two or more can be used in any combination and ratio.

[0254] When the obtained holographic recording medium requires colorless transparency, it is preferable to use anthocyanin pigments as sensitizers. Anthocyanin pigments are generally easily decomposed by light. Therefore, by performing post-exposure, i.e., placing the medium under indoor light or sunlight for several hours to several days, the anthocyanin pigments in the holographic recording medium are decomposed and no longer absorbed in the visible light range, thus obtaining a colorless and transparent holographic recording medium.

[0255] The amount of sensitizer needs to be adjusted according to the thickness of the recording layer to be formed. Preferably, relative to the ratio of the photopolymerization initiator described in 6-2 above, it should be in the range of 0.01% by mass or more, especially 0.1% by mass or more, and typically 10% by mass or less, especially 5% by mass or less. If the amount of sensitizer used is too small, the initiation efficiency may decrease, requiring a long recording time. On the other hand, if the amount of sensitizer used is too large, the absorption of light used for recording or reproduction may increase, making it difficult for light to reach the depth direction. When using two or more sensitizers, their combined dosage should meet the above-mentioned range.

[0256] <Plasticizer> In order to improve reaction efficiency and adjust the physical properties of the recording layer of the holographic recording medium, the polymeric composition of the present invention may also contain a plasticizer.

[0257] Examples of plasticizers include: phthalate esters such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and di(undecyl) phthalate; adipate esters such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate; sebacate esters such as dioctyl sebacate and dibutyl sebacate; phosphate esters such as tricresyl phosphate; citrate esters such as tributyl acetyl citrate; trimellitate esters such as trioctyl trimellitate; alkyl oxidized (poly)alkylene glycol esters such as epoxidized soybean oil, chlorinated paraffin, and acetoxymethoxypropane; and terminal alkyl oxidized polyalkylene glycols such as dimethoxy polyethylene glycol.

[0258] A plasticizer containing fluorine, as illustrated in Japanese Patent No. 6069294, may also be used. Examples of plasticizers containing fluorine include: 2,2,2-trifluoroethyl butyl carbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl)diaminocarbamate, [4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl]diaminocarbamate bis(2,2,2-trifluoroethyl) ester, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononylbutyl carbamate, and 2,2,2-trifluoroethylphenyl carbamate.

[0259] These plasticizers are used in a ratio relative to the total solid content of the polymeric composition in a range typically of 0.01% by mass to 50% by mass, and preferably 0.05% by mass to 20% by mass. If the content of the plasticizer is less than the above range, it will not have the effect of improving reaction efficiency or adjusting physical properties; if the content of the plasticizer is more than the above range, the transparency of the recording layer will decrease, or the exudation of the plasticizer will become significant.

[0260] <Leveling Agent> A leveling agent may be used in the polymeric composition of the present invention. Examples of leveling agents include: sodium polycarboxylate, ammonium polycarboxylate, amine polycarboxylate, silicone-based leveling agents, acrylic-based leveling agents, ester compounds, ketone compounds, fluorine compounds, etc. Any one of these may be used alone, or two or more may be used in any combination and ratio.

[0261] <Chain Transfer Agent> A chain transfer agent may be used in the polymerizable composition of the present invention. Examples of chain transfer agents include: sodium phosphite, sodium hypophosphite, and other phosphonates; mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, thiophene, and other thiols; acetaldehyde, propionaldehyde, and other aldehydes; acetone, methyl ethyl ketone, and other ketones; trichloroethylene, perchloroethylene, and other halogenated hydrocarbons; terpenes such as terpinene, α-terpinene, β-terpinene, and γ-terpinene; 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, 1,4-heptadiene, 1,4-hexadiene, and 2-methyl-1,4-pentadiene. Non-conjugated dienes such as 3,6-nonadien-1-ol and 9,12-octadecadienol; linolenic acids such as alpha-linolenic acid, γ-alpha-linolenic acid, methyl alpha-linolenic acid, ethyl alpha-linolenic acid, isopropyl alpha-linolenic acid, and alpha-linolenic anhydride; linolenic acids such as linolenic acid, methyl linolenic acid, ethyl linolenic acid, isopropyl linolenic acid, and linolenic anhydride; eicosapentaenoic acid and ethyl eicosapentaenoic acid; and docosahexaenoic acid and ethyl docosahexaenoic acid.

[0262] The amount of these additives used, as a ratio relative to the total solid content of the polymeric composition of this embodiment, is preferably set to a range of 0.001% by mass or more, especially 0.01% by mass or more, and typically 30% by mass or less, especially 10% by mass or less. When two or more additives are used together, their total amount shall satisfy the above range.

[0263] 6-5. The composition ratio of each component in the polymeric composition and the content of each component in the polymeric composition of the present invention are arbitrary, as long as they do not violate the spirit of the present invention. The proportions of each component shown below are preferably within the following ranges based on the mole amount per unit mass of the polymeric composition.

[0264] The content of the polymerizable compound comprising the compound of the present invention is preferably 5 μmol / g or more, more preferably 10 μmol / g or more, and even more preferably 100 μmol / g or more. Furthermore, the content of the polymerizable compound is preferably 1000 μmol / g or less, more preferably 500 μmol / g or less, and even more preferably 300 μmol / g or less. By ensuring that the content of the polymerizable compound is at or above the aforementioned lower limit, sufficient diffraction efficiency can be obtained in the holographic recording medium. By ensuring that the content of the polymerizable compound is below the aforementioned upper limit, compatibility with the resin matrix in the recording layer is generally ensured, and the shrinkage of the recording layer caused by recording is kept low.

[0265] When isocyanate and polyol are used as the matrix resin in the polymeric composition of the present invention, the total content of these substances is generally 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, and generally 99.9% by mass or less, preferably 99% by mass or less. By setting this content to the above-mentioned lower limit or above, it is easy to form a recording layer.

[0266] In this case, the ratio of the number of isocyanate reactive functional groups of the polyol to the number of isocyanate isocyanate groups is preferably 0.1 or more, more preferably 0.5 or more, and generally 10.0 or less, more preferably 2.0 or less. By making this ratio within the above range, there are fewer unreacted functional groups, thus improving the stability.

[0267] Furthermore, in this polymerizable composition, the content of the carbamate polymerization catalyst is preferably determined by considering the reaction rate of the isocyanate and the polyol, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 1% by mass or less. It is also preferable to use 0.003% by mass or more.

[0268] The total amount of other components besides the above-mentioned components shall be less than 30% by mass, preferably less than 15% by mass, and even more preferably 5% by mass.

[0269] 6-6. Method for manufacturing polymeric composition In this invention, the method for manufacturing a polymeric composition comprising a polymeric compound, a matrix resin, and a photopolymerization initiator is not particularly limited, and the mixing order can be appropriately adjusted. Furthermore, when the polymeric composition contains components other than those described above, the components can be arbitrarily combined and mixed in any order.

[0270] When isocyanates and polyols are used as matrix resins, the polymerizable composition can be obtained, for example, by the following method, but the present invention is not limited thereto. All components except isocyanates and carbamate polymerization catalysts are mixed, except for the polymerizable compound and the photopolymerization initiator, to prepare a photoreactive composition (liquid A). The mixture of isocyanates and carbamate polymerization catalysts is designated as liquid B. Alternatively, all components except isocyanates can be mixed into the polymerizable compound and the photopolymerization initiator to prepare the photoreactive composition (liquid A).

[0271] It is preferable that each liquid undergoes dehydration and degassing. If dehydration and degassing are insufficient, air bubbles may sometimes be generated during the fabrication of the holographic recording media, resulting in an inability to obtain a uniform recording layer. Heating and depressurization may also be performed during dehydration and degassing, as long as it does not damage the components.

[0272] In the manufacture of the polymerizable composition of liquid A and liquid B, it is preferable to perform the process just before the holographic recording medium is formed. At this time, mixing techniques based on the previous method can also be used. Furthermore, during the mixing of liquid A and liquid B, degassing can be performed as needed to remove residual gases. Moreover, it is preferable that liquid A and liquid B undergo a filtration step separately or after mixing to remove foreign matter and impurities; more preferably, each liquid is filtered separately.

[0273] Alternatively, an isocyanate-functionalized prepolymer can be used as the matrix resin, which is obtained by reacting an isocyanate having an excess of isocyanate groups with a polyol. Furthermore, an isocyanate-reactive prepolymer can also be used as the matrix resin, which is obtained by reacting an isocyanate with a polyol having an excess of isocyanate-reactive functional groups.

[0274] 6-7. Regarding the holographic recording medium of the present invention, the holographic recording medium of the present invention using the polymeric composition of the present invention comprises a recording layer, and may further comprise a support or other layers as needed. Typically, a holographic recording medium has a support, on which the recording layer or other layers are deposited to form the holographic recording medium. However, the holographic recording medium may not have a support when the recording layer or other layers have the strength or durability required by the medium. Examples of other layers include: protective layers, reflective layers, anti-reflective layers (anti-reflective films), etc.

[0275] 6-7-1. Recording Layer The recording layer of the holographic recording medium of the present invention is a layer formed from the polymeric composition of the present invention, and is a layer for recording information. Information is usually recorded in holographic form. As described in the recording method below, a portion of the polymeric compound (hereinafter referred to as polymeric monomer) contained in the recording layer undergoes a chemical change such as polymerization due to holographic recording. Therefore, in the holographic recording medium after recording, a portion of the polymeric monomer is consumed and exists in the form of a compound after reaction, such as a polymer.

[0276] There is no particular limitation on the thickness of the recording layer; it can be determined appropriately by considering the recording method, etc. Preferably, it is 1 μm or more, more preferably 10 μm or more, and more preferably 1 cm or less, and more preferably 3 mm or less. By setting the thickness of the recording layer to the lower limit or above mentioned above, the selectivity of each hologram can often be improved and the degree of multiple recording can be enhanced during multiple recording of holograms. By setting the thickness of the recording layer to the upper limit or below mentioned above, the recording layer can often be uniformly shaped, and multiple recording with uniform diffraction efficiency and a high S / N ratio can be performed.

[0277] Regarding the shrinkage rate of the recording layer caused by exposure during information recording and reproduction, it is preferably below 0.25% for the sake of recording reproducibility.

[0278] 6-7-2. Support Body There are no particular restrictions on the details of the support body, as long as it possesses the strength and durability required for holographic recording media; any support body can be used. The shape of the support body is also unrestricted, typically formed as a flat plate or film. The material constituting the support body is also unrestricted; it can be transparent or opaque.

[0279] If transparent materials are used as the support material, examples include: acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, polycyclic olefin, cellulose acetate, and other organic materials; and glass, silicon, quartz, and other inorganic materials. Among these, polycarbonate, acrylic resin, polyester, amorphous polyolefin, and glass are preferred, especially polycarbonate, acrylic resin, amorphous polyolefin, polycyclic olefin, and glass.

[0280] If an opaque material is used as the material of the support, examples include: metals such as aluminum, metals such as gold, silver, and aluminum coated on the above-mentioned transparent support, or dielectrics such as magnesium fluoride and zirconium oxide.

[0281] There is no particular limitation on the thickness of the support, but it is preferably set to a range of 0.05 mm or more and 1 mm or less. If the thickness of the support is above the lower limit mentioned above, the mechanical strength of the holographic recording medium can be obtained, and the substrate can be prevented from bending. If the thickness of the support is below the upper limit mentioned above, the following advantages can be obtained, such as increased light transmittance, and reduction in the weight or cost of the holographic recording medium.

[0282] The surface of the support may also be surface-treated. This surface treatment is typically used to improve the adhesion between the support and the recording layer. Examples of surface treatments include corona discharge treatment of the support or pre-forming an undercoat on the support. Examples of compositions for the undercoat include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc.

[0283] The surface treatment of the support may also be performed for purposes other than improving adhesion. For example, reflective coating treatment to form a reflective coating made of metals such as gold, silver, or aluminum; dielectric coating treatment to form a dielectric layer such as magnesium fluoride or zirconium oxide. These layers may be formed as a single layer or as two or more layers.

[0284] Such surface treatments can also be provided for the purpose of controlling the permeability of gas or moisture to the substrate. For example, by making the support sandwiching the recording layer also have the function of suppressing the permeability of gas or moisture, the reliability of the holographic recording medium can be improved.

[0285] The support may be provided on either the upper or lower side of the recording layer of the holographic recording medium of the present invention, or it may be provided on both the upper and lower sides. However, when the support is provided on both the upper and lower sides of the recording layer, at least one of the support is made transparent so that active energy lines (excitation light, reference light, regeneration light, etc.) can pass through.

[0286] When a holographic recording medium has a support on one or both sides of the recording layer, it is possible to record a transmissive or reflective hologram. Furthermore, when a support with reflective properties is used on one side of the recording layer, it is possible to record a reflective hologram.

[0287] The support can also be patterned for data addressing. In this case, there are no restrictions on the patterning method. For example, the support itself can be patterned, or a pattern can be formed on the reflective layer described below, or a combination of these methods can be used to form the pattern.

[0288] 6-7-3. Protective Layer The protective layer is used to prevent degradation of the recording and reproduction characteristics of the recording layer. There are no restrictions on the specific composition of the protective layer; any known material can be used. For example, a layer containing water-soluble polymers, organic / inorganic materials, etc., can be formed as the protective layer.

[0289] There are no particular restrictions on the location where the protective layer is formed. For example, it can be formed on the surface of the recording layer, or between the recording layer and the support, or on the outer surface of the support. The protective layer can also be formed between the support and other layers.

[0290] 6-7-4. Reflective Layer The reflective layer is formed when the holographic recording medium is configured as a reflective type. In the case of a reflective holographic recording medium, the reflective layer may be formed between the support and the recording layer, or it may be formed on the outer side of the support; generally, it is preferred to be located between the support and the recording layer. Known materials can be used as the reflective layer, such as a thin film of metal.

[0291] 6-7-5. Anti-reflective film: For any type of transmissive or reflective holographic recording medium, an anti-reflective film may be provided on the side where the information light, reference light, and regenerated light are incident and emitted, or between the recording layer and the support. The anti-reflective film has the function of improving light utilization efficiency and suppressing noise generation. Known anti-reflective films may be used arbitrarily.

[0292] 6-7-6. Method for Manufacturing Holographic Recording Media The method for manufacturing the holographic recording media of the present invention is not limited. For example, the polymeric composition of the present invention can be coated onto a support in a solvent-free state to form a recording layer. In this case, any coating method can be used. Specific examples include spray coating, spin coating, wire rod coating, dip coating, air knife coating, roller coating, doctor blade coating, and doctor blade roller coating.

[0293] When forming a recording layer, especially when forming a recording layer with a relatively thick film, a method of molding by placing it in a mold or a method of coating it onto a release film and then stamping it against the mold can also be used. Alternatively, a coating liquid can be prepared by mixing the polymeric composition of the present invention with a solvent or additives, and the coating liquid can be coated onto a support and dried to form a recording layer. In this case, any method can be used as the coating method, for example, the same method as described above can be used.

[0294] There are no restrictions on the solvent used in the coating solution. Generally, it is preferable to use a solvent that has sufficient solubility for the components used, provides good film properties, and does not penetrate into the support such as the resin substrate. A single solvent may be used alone, or two or more solvents may be used in any combination and ratio. Furthermore, there are no restrictions on the amount of solvent used. Among these, considering coating efficiency and operability, it is preferable to prepare a coating solution with a solid content concentration of about 1 to 100% by mass.

[0295] Examples of solvents include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl pentyl ketone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, propanol, n-butanol, heptanol, hexanol, diacetone alcohol, and furanol; ketol-alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; ether solvents such as tetrahydrofuran and dimethyl ether; halogen solvents such as dichloromethane, dichloroethane, and chloroform; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; and propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether. Propylene glycol solvents such as ether acetate and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and methyl 3-methoxypropionate; perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol; highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; chain hydrocarbon solvents such as n-hexane and n-octane; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tributylcyclohexane, and cyclooctane; or mixtures thereof.

[0296] As a method for manufacturing a holographic recording medium, the following methods may also be cited: a method of manufacturing by coating a polymeric composition that melts due to heat onto a support, cooling and solidifying it to form a recording layer; a method of manufacturing by coating a liquid polymeric composition onto a support and hardening it by thermal polymerization to form a recording layer; a method of manufacturing by coating a liquid polymeric composition onto a support and hardening it by photopolymerization to form a recording layer.

[0297] The holographic recording medium thus manufactured can be in the form of a vertical flat panel or disc, and can be used in three-dimensional image display devices, diffractive optical elements, high-capacity memory, and other applications. In particular, the holographic recording medium of the present invention using the polymeric composition of the present invention has high refractive index modulation and can also be used as a light guide plate for AR glasses.

[0298] 6-7-7. Application of Holographic Recording Media <Application of High-Capacity Memory> The writing (recording) and reading (reproducing) of information in the holographic recording media of the present invention are both performed by light irradiation.

[0299] When recording information, light that may cause a chemical change in polymerizable monomers, that is, light that may cause them to polymerize and produce a change in concentration, is used as object light (also known as recording light).

[0300] For example, in the case of recording information in the form of a volumetric hologram, an object light and a reference light are simultaneously irradiated onto the recording layer, and the object light and the reference light are coherent in the recording layer. Thereby, the coherent light causes the polymerizable monomers in the recording layer to polymerize and change their concentration. As a result, interference fringes create a refractive index difference in the recording layer, and the interference fringes recorded in the recording layer are used to record a hologram in the recording layer.

[0301] When reproducing a volumetric hologram recorded on the recording layer, a prescribed reproduction light (usually a reference light) is irradiated onto the recording layer. The irradiated reproduction light diffracts according to the aforementioned interference fringes. The diffracted light contains the same information as the recording layer, and therefore the information recorded on the recording layer can be reproduced by reading the diffracted light using a suitable detection mechanism.

[0302] The wavelength regions of the object light, the regenerated light, and the reference light can be arbitrary depending on their respective applications, and can be either the visible light region or the ultraviolet light region. Among these lights, suitable examples include: solid-state lasers such as ruby, glass, Nd-YAG, and Nd-YVO4; diode lasers such as GaAs, InGaAs, and GaN; gas lasers such as helium-neon, argon, krypton, excimer, and CO2; and lasers with excellent monochromaticity and directionality, such as dye lasers with pigments.

[0303] There are no restrictions on the amount of irradiation of the object light, the regenerated light, and the reference light. As long as it is within the range that allows for recording and regeneration, the amount of irradiation can be arbitrary. When the amount of irradiation is very low, the chemical change of the polymerizable monomer may be too incomplete and fail to fully exhibit the heat resistance and mechanical properties of the recording layer. Conversely, when the amount of irradiation is very high, the composition of the recording layer (the composition of the polymerizable composition of the present invention) may deteriorate. Therefore, the object light, the regenerated light, and the reference light are irradiated in a range of generally 0.1 J / cm2 or higher and 20 J / cm2 or lower, depending on the composition of the polymerizable composition of the present invention used in the formation of the recording layer, the type of photopolymerization initiator, and the amount of formulation.

[0304] As holographic recording methods, there are polarized collinear holographic recording methods, reference light incident angle multi-weight holographic recording methods, etc. When using the holographic recording medium of the present invention as the recording medium, any of the recording methods can provide good recording quality.

[0305] <Application of AR Glasses Light Guide Plate> For the holographic recording medium of the present invention, similar to the above-mentioned application of large-capacity memory, it records volumetric holograms.

[0306] For a volumetric holoimage recorded on the recording layer, a specified regenerated light is irradiated onto the recording layer. The irradiated regenerated light diffracts according to the aforementioned interference fringes. At this time, even if the wavelength of the regenerated light is not the same as the wavelength of the recording light, diffraction will still occur as long as the Bragg condition is met with the aforementioned interference fringes. Therefore, if interference fringes corresponding to the wavelength of the regenerated light to be diffracted and the incident angle are pre-recorded, diffraction of the regenerated light in a wide wavelength range can be achieved, thereby expanding the display color gamut of AR glasses.

[0307] If the corresponding interference fringes are pre-recorded according to the wavelength and diffraction angle of the regenerated light, the regenerated light incident from the outside of the holographic recording medium can be guided to the inside of the holographic recording medium, or the regenerated light in the waveguide inside the holographic recording medium can be reflected, split, amplified, or reduced, thereby allowing the regenerated light in the waveguide inside the holographic recording medium to be emitted to the outside of the holographic recording medium, thus expanding the viewing angle of the AR glasses.

[0308] The wavelength range of object light and regenerated light can be arbitrary depending on their respective applications, and can be either visible light or ultraviolet light. Among such lights, lasers, etc., are suitable examples. Regenerated light is not limited to lasers, etc., and display devices such as liquid crystal displays (LCDs) and organic light-emitting displays (OLEDs) are also suitable.

[0309] There are no restrictions on the amount of irradiation of the object light, the regenerated light, and the reference light, as long as it is within the range that allows for recording and reproduction. When the irradiation is very low, the chemical change of the polymerizable monomers may be too incomplete to fully exhibit the heat resistance and mechanical properties of the recording layer. Conversely, when the irradiation is very high, the composition of the recording layer (the composition of the polymerizable composition of the present invention) may deteriorate. Therefore, the object light, the regenerated light, and the reference light are irradiated in a range of generally 0.1 J / cm2 or more and 20 J / cm2 or less, depending on the composition of the polymerizable composition of the present invention used in the formation of the recording layer, the type of photopolymerization initiator, and the amount of formulation.

[0310] 6-8. Performance Indicators of Holographic Recording Media The performance of holographic recording media is indicated by the total Δn, calculated from the sum of the diffraction efficiencies of the entire multi-recording system. In the case of a transmitted hologram, the diffraction efficiency of the hologram is given by the ratio of the intensity of the diffracted light to the sum of the intensity of the transmitted light and the intensity of the diffracted light. Using the following formula based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), Δn is calculated from the obtained diffraction efficiency, and the sum of the multiple recordings is taken as the total Δn.

[0311] [Number 1]

[0312] Here, η is the diffraction efficiency, T is the thickness of the medium, λ is the wavelength of the reference light, and θ is the incident angle of the reference light.

[0313] In the case of large-capacity memory, a higher total Δn means that more information can be recorded per unit volume, which is considered better. Furthermore, in the case of AR glasses applications, a higher total Δn means that the projected image from the projector can be clearly transmitted to the eyes, or power consumption can be reduced, or the viewing angle can be expanded, which is also considered better. [Example]

[0314] Hereinafter, the present invention will be described in further detail by way of embodiments. The present invention is not limited to the following embodiments without departing from its spirit.

[0315] The following describes the synthesis method for each compound, including the chemical formula of the synthesis process.

[0316] [Raw Materials Used] The raw materials used in the compositions used in the Examples and Comparative Examples are shown below.

[0317] <Isocyanates> ・Dornex (registered trademark) TSS-100: Hexamethylene diisocyanate-based polyisocyanate (NCO 17.6%) (manufactured by Asahi Kasei Corporation)

[0318] <Polyol> ・PLACCEL PCL-205U: Polycaprolactone Diol (Molecular Weight 530) (Manufactured by Daicel) ・PLACCEL PCL-305: Polycaprolactone Triol (Molecular Weight 550) (Manufactured by Daicel)

[0319] <Photopolymerization Initiator> ・HLI02: Methyl 1-(9-ethyl-6-cyclohexyl-9H-carbazole-3-yl)-1-(O-acetylgoxime)glutarate

[0320] <Free Radical Scavenger> • TEMPOL: 4-Hydroxy-2,2,6,6-Tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Co., Ltd.) <Light Stabilizer> • Adekastab LA-63P (manufactured by ADEKA Co., Ltd.)

[0321] <Carbamate Polymerization Catalyst>・Octolic Acid Solution of Bismuth Tris(2-Ethylhexanoate) (Active Ingredient Amount 56% by Mass)

[0322] (Synthesis Example 1) Using the method described in Japanese Patent Application Publication No. 2017-14213, bis(4-dibenzothiophene) disulfide as compound S-1 and 4-dibenzothiophene mercaptan as compound S-2 were synthesized by the following synthesis method.

[0323] [Chemical 21]

[0324] Dissolve 20 g of dibenzothiophene in 300 mL of THF, cool to 0°C, and simultaneously add 74.6 mL of a 1.6 M n-butyllithium hexane solution. Heat to 20°C and stir for 2 hours. Cool the resulting brown reaction solution to -40°C and add 3.8 g of sulfur (powder, manufactured by Wako Pure Chemicals). Stir at -40°C for 30 minutes, then add 5 mL of water to terminate the reaction. Concentrate the resulting solution using an evaporator, wash the resulting solid with 100 mL of toluene for 30 minutes, and filter to separate the yellow solid, thus preparing compound S-1.

[0325] Compound S-1 was dispersed in 200 mL of THF, and 4.5 g of sodium borohydride was added. The mixture was stirred at 50 °C for 1 hour. The reaction solution was then filtered, and the resulting solution was concentrated using an evaporator. 200 mL of toluene was added. The toluene solution was washed with water, 1 equivalent concentration hydrochloric acid, and 1 equivalent concentration sodium hydroxide aqueous solution, and then concentrated. Recrystallization with hexane yielded 9.4 g (40% yield) of compound S-2.

[0326] A few mL of deuterium chloroform was added to an appropriate amount of compound S-2 (approximately 10 mg) and dissolved. If insoluble fractions were found, the solution was filtered through a cotton plug. The solution was then transferred to a dedicated sample tube and capped. Using this solution, the resonance state of hydrogen was determined in a 400 MHz nuclear magnetic resonance (NMR) instrument. The resonance lines were assigned to hydrogen atoms of the compound, confirming the acquisition of the target compound. The measurement data are shown below. Measurements were also performed on the target compounds described below, confirming their acquisition. The measurement data are shown below. 1H NMR (400 MHz, CDCl3, δ, ppm) 3.63 (s, 1H), 7.35 (Ar, 1H), 7.45 (Ar, 3H), 7.89 (Ar, 1H), 8.05 (Ar, 1H), 8.14 (Ar, 1H)

[0327] (Example 1) Compound M-1 was manufactured by the following synthetic method.

[0328] [Chemistry 22]

[0329] Under a nitrogen atmosphere, compound S-2 (20 g), 2,2-bis(bromomethyl)-1,3-propanediol (12.11 g), and DMF (150 mL) were mixed. Here, a solution of potassium tert-butoxide (10.37 g) in DMF (50 mL) was added dropwise at 75°C, followed by stirring for 30 minutes.

[0330] After the reaction was completed, the reaction solution was injected into 1 L of water, extracted twice with 500 mL of ethyl acetate, washed with 1 L of saturated brine, dried with sodium sulfate, filtered, and concentrated. The crude product was purified by silicone column chromatography to obtain 9.7 g (yield 97%) of compound S-3.

[0331] The NMR data of compound S-3 are shown below. ¹H-NMR (400 M Hz, CDCl₃) δ 8.31 - 8.29 (m, 2H), 8.15 (d, J = 9.5 Hz, 2H), 7.99 - 7.97 (m, 2H), 7.53 - 7.50 (m, 6H), 7.39 (t, J = 3.5 Hz, 2H), 4.78 (t, J = 4.8 Hz, 2H), 3.51 (d, J = 4.8 Hz, 4H), 3.27 (s, 4H).

[0332] Under a nitrogen atmosphere, compound S-3 (3.0 g), sodium tributoxide (0.80 g), and THF (30 mL) were mixed. Here, 2-chloro-1,3-benzothiazole (1.34 g) was added dropwise at 30°C over 1 hour, followed by stirring for 1 hour. After the reaction was complete, the reaction mixture was added to 50 mL of water, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried with anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silicone column chromatography to obtain 1.9 g (51% yield) of compound S-4.

[0333] The NMR data for compound S-4 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.14 (t, OH, ¹H), 3.38 (d, 2H), 3.40 (d, 2H), 3.71 (d, 2H), 4.63 (s, 2H), 7.20 (Ar, ¹H), 7.29 (Ar, 3H), 7.45 (Ar, 5H), 7.53 (Ar, 3H), 7.82 (Ar, 4H), 8.00 (Ar, 2H)

[0334] Compound S-4 (1.9 g) was dissolved in 15 mL of dichloromethane, and 19 mg of dibutyltin diacetate was added. 0.65 g of ethyl 2-isocyanate acrylate was added to this solution, and the reaction was carried out at room temperature for approximately 50 hours. After the reaction was complete, 20 mL of dichloromethane was added, and the solution was passed through a silicone short-pass column and concentrated to a total volume of 10 g at below 30°C. This solution was added dropwise to 100 mL of ice-cold methanol, and stirred directly for 1 hour. The precipitate was filtered, washed with methanol, and dried to obtain 1.6 g (71% yield) of compound M-1.

[0335] The NMR data for compound M-1 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.29 (m, 2H), 3.40 (s, 4H), 4.09 (m, 2H), 4.29 (s, 2H), 4.53 (s, 2H), 4.64 (brt, NH, 1H), 5.80 (dd, 1H), 6.06 (dd, 1H), 6.37 (dd, 1H), 7.17 (Ar, 1H), 7.22 (Ar, 2H), 7.26 (Ar, 1H), 7.36 (Ar, 1H), 7.44 (Ar, 5H), 7.52 (Ar, 2H), 7.79 (Ar, 4H), 7.94 (Ar, 2H)

[0336] <Production of Holographic Recording Media> Solution A was prepared by dissolving 0.269 g of compound M-1 (as a polymerizable monomer), 0.0096 g of photopolymerization initiator HLI02, 3.30 mg of free radical scavenger TEMPOL, and 2.6 mg of light stabilizer LA-63P in 2.53 g of Dornex (registered trademark) TSS-100. Solution B was prepared by mixing 1.73 g of PLACEL PCL-205U and 0.74 g of PLACEL PCL-305 (PLACCEL PCL-205U:PLACCEL PCL-305 = 70:30 (mass ratio)) and dissolving 0.2 mg of a bismuth tris(2-ethylhexanoate) octanoic acid solution.

[0337] After degassing solutions A and B separately at room temperature or 45°C under reduced pressure for 2 hours, 2.39 g of solution A and 2.11 g of solution B were stirred and mixed, and then degassed under vacuum for several minutes. The vacuum-degassed mixture was then poured onto a glass slide with 0.5 mm thick spacers placed at opposite ends, and a glass slide was placed on top. The perimeter was fixed using clamps, and the mixture was heated at 80°C for 24 hours to create a holographic recording medium for evaluation. This evaluation sample has a 0.5 mm thick recording layer formed between the glass slides serving as the outer cover.

[0338] The holographic recording medium is formulated with a ratio of isocyanate base in solution A to isocyanate reactive base in solution B of 1.0, with a polymerizable monomer of 58.3 μmol / g, a photopolymerization initiator of 3.05 μmol / g, and a free radical scavenger of 3.05 μmol / g.

[0339] [Holographic Recording and Evaluation Methods] Holographic recording and evaluation of the holographic recording performance of the holographic recording media were performed using holographic recording media prepared as evaluation samples in the order described below.

[0340] Holographic recording uses a semiconductor laser with a wavelength of 405 nm and the exposure apparatus shown in Figure 1 to perform holographic recording of two-beam plane waves at an exposure power density of 10.2 mW / cm² per beam. The medium is rotated from -22.5° to 22.5°, and multiple recordings are performed at the same location. The diffraction efficiency during each multiple recording is measured. Δn is calculated based on the obtained diffraction efficiency, and the sum of the total diffraction efficiency across all multiple recordings is taken as the total Δn. This will be explained in detail below.

[0341] (Holographic Recording) Figure 1 is a schematic diagram showing the general structure of the apparatus used for holographic recording. In Figure 1, S is a sample of the holographic recording medium, and M1 to M3 all represent mirrors. PBS represents a polarizing beam splitter, and L1 represents a recording light source emitting light at a wavelength of 405 nm (a single-mode laser manufactured by TOPTICA Photonics that can obtain light near a wavelength of 405 nm (L1 in Figure 1)). L2 represents a regenerating light source emitting light at a wavelength of 633 nm. PD1, PD2, and PD3 represent photodetectors. 1 represents an LED unit.

[0342] As shown in Figure 1, a 405 nm wavelength light is split by a polarizing beam splitter (PBS in the figure) and made to intersect on the recording plane, so that the angle between the two beams reaches 59.3°. At this time, the two bisectors of the angle between the two beams are perpendicular to the recording plane, and the vibration plane of the electric field vectors of the two beams obtained by splitting is made perpendicular to the plane containing the intersecting two beams for illumination.

[0343] After holographic recording, a device that can obtain light with a wavelength of 633 nm using a He-Ne laser (V05-LHP151 manufactured by Melles Griot: "L2" in the figure) is used to illuminate the holographic recording medium at an angle of 50.7°. The diffracted light is detected using a photodiode and a photosensor amplifier (S2281 and C9329 manufactured by Hamamatsu Photonics: "PD1" in the figure) to determine whether the holographic recording was performed correctly.

[0344] (Determination of diffraction efficiency) The angle of the sample relative to the optical axis (the angle between the bisecting line of the interior angle of the intersection of the two beams, i.e. the incident beams incident from mirrors M1 and M2 in Figure 1, and the sample normal) was moved from -22.5° to 22.5° in a manner of 0.3° each time, and 151 multiple records were made.

[0345] After multiple recordings, the LED unit (1 in the figure, center wavelength 405 nm) is lit for a certain period of time to consume the remaining initiator and monomer. This step is called post-exposure. The LED power is set to 100 mW / cm2, and irradiation is performed with a cumulative energy of 12 J / cm2.

[0346] The diffraction efficiency of a hologram is given by the ratio of the diffracted light intensity to the sum of the transmitted light intensity and the diffracted light intensity. Light (wavelength 405 nm) from mirror M1 in Figure 1 was used to illuminate the image, and the diffraction efficiency was measured from an angle of -23° to 23°. Δn was calculated from the obtained diffraction efficiency using the following formula based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum of these values ​​across multiple records was taken as the total Δn.

[0347] [Number 2]

[0348] Here, η is the diffraction efficiency, T is the media thickness, λ is the wavelength of the reference light, and θ is the incident angle of the reference light (29.65°).

[0349] Using multiple prepared samples, the irradiation energy conditions were varied to conduct multiple evaluations, such as increasing or decreasing the initial irradiation energy during recording, or increasing or decreasing the total irradiation energy, to explore the condition that would deplete the polymerizable monomers (total Δn would approximately reach equilibrium during multiple recordings), thereby maximizing the total Δn. Then, the obtained maximum value was set as the total Δn of the medium.

[0350] (Measurement of transmittance before and after recording) The transmittance before recording is determined by measuring the ratio of the transmitted light power to the incident light power of the evaluation sample before recording. Furthermore, the transmittance after recording is determined by measuring the ratio of the transmitted light power to the incident light power of the evaluation sample after post-exposure.

[0351] (Determination of Haze After Recording) Using evaluation samples that underwent holographic recording and post-exposure, the haze value against white light was measured using a haze meter NDH 7000SPII manufactured by Nippon Denshoku Kogyo Co., Ltd. (JIS K7136). Furthermore, the ratio of this haze value to the aforementioned total Δn (haze% / total Δn) was calculated. The lower this ratio, the higher the balance between diffraction efficiency and transparency.

[0352] (Example 2) Compound M-2 was manufactured by the following synthesis method.

[0353] [Chemical 23]

[0354] 10 g of pentaerythritol tribromide and 12.8 g of potassium carbonate were suspended in 50 mL of ethanol. The reaction mixture was heated to 100 °C, and the reaction was confirmed by TLC and HPLC while stirring for 4 hours. After cooling the mixture to room temperature, 12.2 g of 2-bromothiophenol was slowly added. The white suspension was heated again to 100 °C and stirred for 1 hour. After cooling to room temperature, the white solid was filtered and washed with 100 mL of ethyl acetate. The obtained organic layer was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 12.4 g (88% yield) of compound S-5.

[0355] The NMR data for compound S-5 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.50 (s, 4H), 4.49 (s, 4H), 7.04 (ddd, Ar, 2H), 7.24 (ddd, Ar, 2H), 7.38 (dd, Ar, 2H), 7.53 (dd, Ar, 2H)

[0356] Compound S-5 (3 g), dibenzothiophene-4-boronic acid (4.5 g), and potassium phosphate (5.5 g) were suspended in 20 mL of toluene, 10 mL of ethanol, and 10 mL of water, and degassed by purging with nitrogen. 138 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was then purged for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After filtration through diatomaceous earth, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 4.4 g of crude compound S-6.

[0357] The NMR data for compound S-6 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.01 (s, 4H), 4.03 (s, 4H), 7.17 (Ar, 2H), 7.27 (Ar, 4H), 7.35 (Ar, 4H), 7.45 (Ar, 6H), 7.76 (Ar, 2H), 8.16 (Ar, 4H)

[0358] Compound S-6 (4 g), 2-mercaptobenzothiazole (1.2 g), and p-toluenesulfonic acid monohydrate (30 mg) were suspended in 50 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product obtained was purified using a silicone column (hexane / ethyl acetate) to give 4.1 g (82% yield) of compound S-7.

[0359] The NMR data for compound S-7 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.69 (brs, 2H), 2.93 (d, 2H), 3.14 (brs, 4H), 5.04 (s, OH, 1H), 7.27 (Ar, 7H), 7.34 (Ar, 3H), 7.44 (Ar, 8H), 7.65 (Ar, 2H), 7.74 (Ar, 2H), 8.14 (Ar, 4H)

[0360] Compound S-7 (5 g) was dissolved in 15 mL of dichloromethane, and 100 mg of dibutyltin dilaurate was added. 0.85 g of ethyl 2-isocyanate (manufactured by Showa Denko Co., Ltd., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.3 g of ethyl 2-isocyanate was added, and the reaction was carried out for another 24 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by 50 mL of chloroform for extraction. The resulting organic layer was dried with magnesium sulfate and concentrated at below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 3.6 g (62% yield) of compound M-2.

[0361] The NMR data of compound M-2 are shown below. 1H NMR (400 MHz, CDCl3, δ, ppm) 2.77 (brs, 4H), 3.12 (dd, 2H), 3.25 (brs, 2H), 3.78 (brs, 2H), 4.02 (dd, 2H), 4.42 (brs, NH, 1H), 5.83 (d, 1H), 6.10 (dd, 1H), 6.40 (d, 1H), 5.04 (s, OH, 1H), 7.23 (Ar, 5H), 7.31 (Ar, 5H), 7.37 (Ar, 2H), 7.43 (Ar, 6H), 7.63 (Ar, 2H), 7.73 (Ar, 2H), 8.12 (Ar, 4H)

[0362] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-2 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0363] (Example 3) Compound M-3 was manufactured by the following synthesis method.

[0364] [Chemical 24]

[0365] 10 g of bis(bromomethyl)oxetane, 16.3 g of 2-bromothiophenol, and 28 g of cesium carbonate were suspended in 300 mL of methyl ethyl ketone (MEK). The reaction mixture was heated to 90 °C, and the reaction was confirmed by LC analysis while stirring under reflux for 3 hours. After cooling the mixture to room temperature, it was extracted twice with 600 mL of water and 300 mL of ethyl acetate. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 26.5 g (96% yield) of compound S-5. The NMR data of compound S-5 obtained are as described above.

[0366] Compound S-5 (9 g), thiam-1-boronic acid (11.2 g), dichlorobis[triphenylphosphino]palladium(II) (1.37 g), and potassium hydroxide (11 g) were suspended in 90 mL of tetrahydrofuran and 23 mL of water, and degassed by purging with nitrogen. The reaction solution was heated to 80 °C and stirred for 12 hours under a nitrogen atmosphere. After cooling to room temperature, 125 mL of ethyl acetate was added, and the mixture was extracted with 250 mL of water. The resulting organic layer was combined with another batch of organic layers that had undergone the same reaction, concentrated, and purified using a silicone column (heptane-ethyl acetate) to obtain 16 g (66% yield) of compound S-8.

[0367] The NMR data for compound S-8 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.97 (brs, 4H), 3.95 (m, 4H), 7.10 (Ar, 4H), 7.17 (Ar, 4H), 7.23 (Ar, 2H), 7.29 (Ar, 4H), 7.33 (Ar, 2H), 7.36 (Ar, 2H), 7.47 (Ar, 2H), 7.51 (Ar, 2H)

[0368] Compound S-8 (9.5 g), 2-mercaptobenzothiazole (2.4 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 30 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 10.3 g (88% yield) of compound S-9.

[0369] The NMR data for compound S-9 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.55 (dd, 2H), 2.68 (dd, 2H), 2.82 (dd, 2H), 3.04 (d, 2H), 5.04 (brs, OH, 1H), 5.83 (d, 1H), 6.10 (dd, 1H), 6.40 (d, 1H), 5.04 (s, OH, 1H), 7.11 (Ar, 5H), 7.28 (Ar, 5H), 7.43 (Ar, 12H), 7.70 (Ar, 4H)

[0370] Compound S-9 (6.3 g) was dissolved in 30 mL of dichloromethane, and 100 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate (1.1 g) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.5 g of ethyl 2-isocyanate was added, and the reaction was carried out for another 24 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by extraction with 50 mL of chloroform. The resulting organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 5.1 g (70% yield) of compound M-3.

[0371] The NMR data for compound M-3 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.71 (m, 4H), 3.13 (d, 1H), 3.23 (m, 3H), 3.77 (m, 2H), 4.08 (m, 2H), 4.69 (brs, NH, 1H), 5.83 (d, 1H), 6.10 (dd, 1H), 6.41 (d, 1H), 7.12 (Ar, 10H), 7.35 (Ar, 14H), 7.73 (Ar, 2H)

[0372] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-3 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0373] (Example 4) Compound M-4 was manufactured by the following synthesis method.

[0374] [Chemical 25]

[0375] 10 g of pentaerythritol tribromide and 12.8 g of potassium carbonate were suspended in 50 mL of ethanol. The reaction mixture was heated to 100 °C, and the reaction was confirmed by TLC while stirring for 4 hours. After cooling the mixture to room temperature, 11.6 g of 3-bromothiophenol was slowly added. The white suspension was heated again to 100 °C and stirred for 1 hour. After cooling to room temperature, the white solid was filtered and washed with 100 mL of ethyl acetate. The obtained organic layer was concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 11.8 g (83% yield) of compound S-10.

[0376] The NMR data for compound S-10 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.44 (s, 4H), 4.43 (s, 4H), 7.12 (dd, 2H), 7.27 (Ar, 2H), 7.31 (Ar, 2H), 7.49 (dd, 2H)

[0377] Compound S-10 (2 g), dibenzothiophene-4-boronic acid (3.9 g), and potassium phosphate (4.6 g) were suspended in 20 mL of toluene, 10 mL of ethanol, and 10 mL of water, and degassed by purging with nitrogen. 31 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After filtration through diatomaceous earth, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 2.9 g of crude compound S-11.

[0378] The NMR data for compound S-11 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.57 (s, 4H), 4.51 (s, 4H), 7.36 (Ar, 4H), 7.45 (Ar, 10H), 7.74 (Ar, 4H), 8.09 (dd, 2H), 8.14 (Ar, 2H)

[0379] Compound S-11 (2.9 g), 2-mercaptobenzothiazole (0.87 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 50 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 2.8 g (76% yield) of compound S-12.

[0380] The NMR data for compound S-12 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.23 (d, 2H), 3.44 (d, 2H), 3.64 (brd, 2H), 3.68 (s, 2H), 5.47 (brt, OH, 1H), 7.30 (ddd, 1H), 7.39 (Ar, 8H), 7.48 (Ar, 7H), 7.70 (d, 1H), 7.76 (Ar, 5H), 8.10 (dd, 2H), 8.15 (brd, 2H)

[0381] Compound S-12 (2.7 g) was dissolved in 15 mL of dichloromethane, and 60 mg of dibutyltin diacetate was added. 0.55 g of ethyl 2-isocyanate acrylate (manufactured by Showa Denko Co., Ltd., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.2 g of ethyl 2-isocyanate acrylate was added, and the reaction was carried out for another 24 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by 50 mL of chloroform for extraction. The resulting organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 1.5 g (48% yield) of compound M-4.

[0382] The NMR data for compound M-4 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.21 (dd, 2H), 3.39 (s, 4H), 3.84 (s, 2H), 4.01 (dd, 2H), 4.30 (s, 2H), 4.76 (brt, NH, 1H), 5.69 (d, 1H), 5.92 (dd, 1H), 6.29 (d, 1H), 7.21 (dd, 1H), 7.31 (Ar, 3H), 7.44 (Ar, 12H), 7.62 (brd, 1H), 7.76 (Ar, 5H), 8.11 (dd, 2H), 8.15 (brd, 2H)

[0383] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-4 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0384] (Example 5) Compound M-5 was manufactured by the following synthesis method.

[0385] [Chemical 26]

[0386] 20 g of bis(bromomethyl)oxetane, 32.6 g of 3-bromothiophenol, and 56.1 g of cesium carbonate were suspended in 600 mL of methyl ethyl ketone (MEK). The reaction mixture was heated to 90 °C, and the reaction was confirmed by LC analysis while stirring under reflux for 3 hours. After cooling the mixture to room temperature, it was extracted twice with 600 mL of water and 300 mL of ethyl acetate. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 35 g (94% yield) of compound S-10. The NMR data of the obtained compound S-10 are as described above.

[0387] Compound S-10 (29.2 g), thiam-1-boronic acid (36.3 g), dichlorobis[triphenylphosphino]palladium(II) (4.45 g), and potassium hydroxide (35.6 g) were suspended in 360 mL of tetrahydrofuran and 90 mL of water, and degassed by purging with nitrogen. The reaction solution was heated to 80 °C and stirred for 12 hours under a nitrogen atmosphere. After cooling to room temperature, 200 mL of ethyl acetate was added, and the mixture was extracted with 450 mL of water. The organic layer was concentrated, and the crude product was purified using a silicone column (heptane-ethyl acetate) to obtain 33.4 g (66% yield) of compound S-13.

[0388] The NMR data for compound S-13 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.56 (s, 4H), 4.48 (s, 4H), 7.14 (Ar, 4H), 7.21 (Ar, 6H), 7.33 (Ar, 4H), 7.43 (Ar, 4H), 7.49 (Ar, 4H)

[0389] Compound S-13 (8.5 g), 2-mercaptobenzothiazole (2.3 g), and toluenesulfonic acid monohydrate (50 mg) were suspended in 130 mL of toluene. The reaction solution was heated to 110 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, 100 mL of toluene was added, and the mixture was washed with 1 M sodium hydroxide aqueous solution. The organic layer was then washed with 0.1 N hydrochloric acid and then washed again with water. Chloroform was added to dissolve the insoluble matter in the organic layer, and the mixture was dried and concentrated using anhydrous magnesium sulfate. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 7.9 g (76% yield) of compound S-14.

[0390] The NMR data for compound S-14 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.22 (d, 2H), 3.42 (d, 2H), 3.63 (d, 2H), 3.67 (s, 2H), 5.46 (t, OH, 1H), 7.09 (ddd, 2H), 7.20 (Ar, 8H), 7.29 (ddd, 1H), 7.30 (d, 2H), 7.34 (d, 2H), 7.40 (ddd, 1H), 7.47 (Ar, 8H), 7.69 (Ar, 1H), 7.77 (Ar, 1H)

[0391] Compound S-14 (4.0 g) was dissolved in 40 mL of dichloromethane, and 38 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (1.1 g) was added to the solution, and the reaction was carried out at room temperature for 50 hours. After the reaction was completed, the solution was concentrated at a temperature below 30°C, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 3.6 g (80% yield) of compound M-5.

[0392] The NMR data of compound M-5 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 3.24 (m, 2H), 3.37 (s, 4H), 3.83 (s, 2H), 4.04 (m, 2H), 4.28 (s, 2H), 4.89 (brt, NH, 1H), 5.74 (d, 1H), 5.94 (dd, 1H), 6.31 (d, 1H), 7.12 (Ar, 6H), 7.20 (Ar, 4H), 7.27 (Ar, 5H), 7.33 (ddd, 1H), 7.40 (Ar, 4H), 7.48 (Ar, 4H), 7.65 (Ar, 1H), 7.77 (Ar, 1H)

[0393] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-5 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0394] (Example 6) Compound M-6 was manufactured by the following synthesis method.

[0395] [Chemical 27]

[0396] 1.0 g of 1,1'-bi-2-naphthol, 1.0 g of bis(bromomethyl)oxetane, and 1.2 g of cesium carbonate were suspended in 8 mL of N,N-dimethylformamide (DMF). The reaction mixture was heated to 120°C and stirred for 3 hours. After cooling to room temperature, the resulting white solid was filtered, washed with methanol, and dried under reduced pressure to obtain 1.3 g of compound S-15.

[0397] The NMR data for compound S-15 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.28 (d, 2H), 4.39 (d, 2H), 4.49 (d, 2H), 4.76 (d, 2H), 7.21 (Ar, 4H), 7.37 (Ar, 2H), 7.55 (d, 2H), 7.87 (d, 2H), 7.95 (d, 2H)

[0398] Compound S-15 (5.0 g), 2-mercaptobenzothiazole (2.3 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 20 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 5.5 g (78% yield) of compound S-16.

[0399] The NMR data of compound S-16 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 3.34 (m, 3H), 3.51 (d, 1H), 4.08 (d, 1H), 4.32 (d, 1H), 4.54 (brd, 1H), 4.82 (brd, 1H), 5.58 (t, OH, 1H), 7.21 (Ar, 2H), 7.27 (Ar, 2H), 7.31 (Ar, 1H), 7.38 (Ar,3H), 7.45 (d, 1H), 7.58 (d, 1H), 7.72 (d, 1H), 7.78 (d, 1H), 7.89 (Ar, 2H), 7.98 (Ar, 2H)

[0400] Compound S-16 (2.5 g) was suspended in 16 mL of dichloromethane, and 29 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.98 g) was added to the solution, and the reaction was carried out at 30°C for 30 hours. After the reaction was completed, the solution was concentrated at a temperature below 30°C, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 2.0 g (70% yield) of compound M-6.

[0401] The NMR data of compound M-6 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 3.37 (m, 2H), 3.42 (d, 1H), 3.52 (d, 1H), 3.95 (d, 1H), 4.05 (d, 1H), 4.17 (m, 2H), 4.31 (d, 1H), 4.49 (s, 2H), 4.69 (d, 1H), 4.95 (brt, NH, 1H), 5.83 (d, 1H), 6.11 (dd, 1H), 6.41 (d, 1H), 7.22 (Ar, 4H), 7.28 (Ar, 1H), 7.36 (Ar, 3H), 7.45 (d, 1H), 7.51 (d, 1H), 7.66 (d, 1H), 7.72 (d, 1H), 7.78 (d, 1H), 7.86 (Ar, 2H), 7.95 (d, 1H)

[0402] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-6 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0403] (Example 7) Compound M-7 was manufactured by the following synthesis method.

[0404] [Chemical 28]

[0405] 1.4 g of 9H-carbazole, 1.0 g of bis(bromomethyl)oxetane, 0.66 g of sodium hydroxide, and 20 mg of benzyltrimethylammonium bromide were suspended in 5 mL of diethylene glycol dimethyl ether. The reaction mixture was heated to 120 °C and stirred for 3 hours. After cooling to room temperature, the resulting white solid was filtered, washed with methanol, and dried under reduced pressure to obtain 1.3 g (76% yield) of compound S-17.

[0406] The NMR data for compound S-17 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.64 (s, 4H), 4.69 (s, 4H), 7.27 (Ar, 8H), 7.43 (Ar, 4H), 8.13 (brd, 4H)

[0407] Compound S-17 (5.3 g), 2-mercaptobenzothiazole (2.1 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 30 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was washed with a small amount of methanol to give 6.9 g (94% yield) of compound S-18.

[0408] The NMR data for compound S-18 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.89 (s, 2H), 4.18 (d, 2H), 4.50 (d, 2H), 4.88 (d, 2H), 5.20 (t, OH, 1H), 7.25 (Ar, 5H), 7.44 (Ar, 9H), 7.61 (d, 1H), 7.82 (d, 1H), 8.11 (brd, 4H)

[0409] Compound S-18 (3.8 g) was dissolved in 30 mL of tetrahydrofuran, and 28 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (1.0 g) was added to the solution, and the reaction was carried out at room temperature. After 48 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with 50 mL of chloroform. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 3.4 g (72% yield) of compound M-7.

[0410] The NMR data of compound M-7 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 3.24 (m, 2H), 3.75 (m, 2H), 3.99 (s, 2H), 4.06 (t, 2H), 4.40 (t, OH, 1H), 4.43 (s, 2H), 4.68 (d, 2H), 4.73 (d, 2H), 5.86 (d, 1H), 6.13 (dd, 1H), 6.42 (d, 1H), 7.23 (Ar, 4H), 7.29 (Ar, 1H), 7.39 (Ar, 9H), 7.72 (d, 1H), 7.80 (d, 1H), 8.08 (d, 4H)

[0411] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-7 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0412] (Example 8) Compound M-8 was manufactured by the following synthesis method.

[0413] [Chemistry 29]

[0414] Compound S-3 (2.0 g) obtained in Example 1 was dissolved in 8 mL of tetrahydrofuran under an atmosphere, and 32 mL of dichloromethane and 26 mg of dibutyltin diacetate were added. 1.3 g of 2-bromophenyl isocyanate was divided into 3 portions and added to the solution, and the reaction was carried out at an internal temperature of 5°C for 5 hours. After the reaction was completed, the solvent was removed by vacuum distillation, and the crude product was purified using a silicone column to obtain 1.85 g (68% yield) of compound S-19.

[0415] The NMR data for compound S-19 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.29 (t, OH, ¹H), 3.33 (s, CH₂, 4H), 3.68 (d, CH₂, 2H), 4.29 (s, CH₂, 2H), 6.79 (s, NH, ¹H), 6.91 (Ar, ¹H), 7.24 (Ar, ¹H), 7.32 (Ar, 2H), 7.40 - 7.48 (Ar, 5H), 7.54 (Ar, 2H), 7.82 (Ar, 2H), 7.92 (Ar, 2H), 7.95 (Ar, ¹H), 8.02 (Ar, 2H)

[0416] Compound S-19 (1.84 g), dibenzothiophene-4-boronic acid (1.21 g), and potassium phosphate (1.28 g) were suspended in 14 mL of toluene, 14 mL of ethanol, and 7 mL of water, and degassed by purging with nitrogen. 34 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with 1 N NaOH aqueous solution. The solution was then washed with water and brine, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified using a silicone column to obtain 1.8 g (89% yield) of compound S-20.

[0417] The NMR data for compound S-20 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.65 (t, OH, 1H), 2.81 - 3.28 (br, CH₂, 4H), 3.49 (d, CH₂, 2H), 4.14 (br, CH₂, 2H), 6.25 (s, NH, 1H), 6.95 - 7.53 (Ar, 15H); 7.70 - 7.85 (Ar, 5H), 7.94 - 8.05 (Ar, 3H), 8.07 - 8.15 (Ar, 2H)

[0418] Compound S-20 (1.7 g) was dissolved in 17 mL of dichloromethane, and 16 mg of dibutyltin diacetate was added. 0.42 g of ethyl 2-isocyanate acrylate was added to the solution, and the reaction was carried out at room temperature for approximately 72 hours. After the reaction was complete, the solution was purified using a silicone column (dichloromethane / ethyl acetate), and the obtained fraction was concentrated to a total volume of 10 g at a temperature below 30°C. This solution was added dropwise to 100 mL of ice-cold methanol, and stirred directly for 1 hour. The precipitate was filtered, washed with methanol, and dried to obtain 1.2 g (68% yield) of compound M-8.

[0419] The NMR data of compound M-8 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 2.92 - 3.20 (brm, CH2, 4H), 3.24 (brq, CH2, 2H), 3.84 - 4.16 (brm, CH2, 4H), 4.20 (s, CH2, 2H), 4.55 (brt, NH, 1H), 5.79 (dd, 1H), 6.05 (dd, 1H), 6.24 (s, NH, 1H), 6.37 (dd, 1H), 7.11 - 7.25 (Ar, 5H), 7.30 - 7.48 (Ar, 10H), 7.71 - 7.81 (Ar, 3H), 7.85 (Ar, 2H), 7.95 - 8.06 (Ar, 3H), 8.07 - 8.14 (Ar, 2H)

[0420] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-8 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0421] (Example 9) Compound M-9 was manufactured by the following synthesis method.

[0422] [Chemistry 30]

[0423] Under a nitrogen atmosphere, 8.1 g of pentaerythritol dibromide was dissolved in 80 mL of methyl ethyl ketone (MEK), and 12.9 g of 2-bromothiophenol and 9.2 g of potassium carbonate were added. The mixture was reacted under reflux for 4 hours. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate, washed with 1 N sodium hydroxide solution, and then washed with brine. The resulting solution was dried over anhydrous magnesium sulfate and concentrated, and then purified using a silicone column (dichloromethane, ethyl acetate) to obtain 13.4 g (89% yield) of compound S-21.

[0424] The NMR data for compound S-21 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.13 (t, OH, 2H), 3.16 (s, CH₂, 4H), 3.82 (d, CH₂, 4H), 7.02 (Ar, 2H), 7.24 (Ar, 2H), 7.38 (Ar, 2H), 7.52 (Ar, 2H)

[0425] Compound S-21 (5.2 g) was dissolved in 75 mL of dichloromethane, and 22 mg of triethylamine was added. 2.3 g of 2-bromophenyl isocyanate was divided into three portions and added to the solution, and the reaction was carried out at room temperature for 7 hours. The reaction was terminated by adding water. After separation, the organic layer was washed with 0.1 N hydrochloric acid and water. The resulting solution was dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 3.4 g (47% yield) of compound S-22.

[0426] The NMR data for compound S-22 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.51 (t, OH, ¹H), 3.19 (m, CH₂, 4H), 3.69 (d, CH₂, 2H), 4.33 (s, CH₂, 2H), 6.96 - 7.03 (Ar, 4H), 7.20 - 7.35 (Ar, 3H), 7.40 - 7.43 (Ar, 2H), 7.50 - 7.55 (Ar, 3H), 8.05 (brd, NH, ¹H)

[0427] Compound S-22 (3.3 g), dibenzothiophene-4-boronic acid (3.7 g), and potassium phosphate (3.6 g) were suspended in 24 mL of toluene, 24 mL of ethanol, and 12 mL of water, and degassed by purging with nitrogen. 101 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with a 1 N sodium hydroxide aqueous solution. The solution was then washed with water and brine, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 4.1 g (88% yield) of compound S-23.

[0428] The NMR data for compound S-23 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.24 (brs, OH, ¹H), 2.54 (brd, CH₂, 4H), 3.02 (d, CH₂, 2H), 3.76 (brs, CH₂, 2H), 6.18 (s, NH, ¹H), 6.98 - 7.27 (Ar, ¹¹H), 7.31 - 7.49 (Ar, ¹¹H), 7.53 (Ar, ¹H), 7.67 - 7.75 (Ar, ³H), 7.94 (Ar, ¹H), 8.07 (Ar, 2H), 8.14 (Ar, 2H), 8.16 - 8.22 (Ar, 2H)

[0429] Compound S-23 (4.1 g) was dissolved in 40 mL of dichloromethane, and 36 mg of dibutyltin diacetate was added. 0.97 g of ethyl 2-isocyanate acrylate was added to the solution, and the reaction was carried out at room temperature for approximately 72 hours. After the reaction was complete, the solution was purified using a silicone column (dichloromethane, ethyl acetate), and the obtained fraction was concentrated to a total volume of 20 g at a temperature below 30°C. This solution was added dropwise to 350 mL of ice-cold methanol, and stirred directly for 2 hours. The precipitate was filtered, washed with methanol, and dried to obtain 3.4 g (72% yield) of compound M-9.

[0430] The NMR data of compound M-9 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 2.52 (brs, CH2, 4H), 2.88+3.16 (brs+d, CH2, 2H), 3.60 (brs, CH2, 2H), 3.75 (s, CH2, 2H), 3.85+4.03 (brs+t, CH2, 2H), 4.39 (brs, NH, 1H), 5.81 (d, 1H), 6.08(dd, 1H), 6.18 (s, NH, 1H), 6.39 (d, 1H), 7.03 - 7.34 (Ar, 12H), 7.34 - 7.55 (Ar, 11H), 7.68 - 7.76 (Ar, 3H), 7.98 (Ar, 1H), 8.07 (Ar, 2H), 8.12 - 8.19 (Ar, 4H)

[0431] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-9 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0432] (Example 10) Compound M-10 was manufactured by the following synthesis method.

[0433] [Chemistry 31]

[0434] Compound S-21 (3.0 g) obtained in Example 9 was dissolved in 45 mL of dichloromethane, and 12 mg of triethylamine was added. 2.0 g of 3-bromophenyl isocyanate was divided into three portions and added to the solution, and the reaction was carried out at room temperature for 12 hours. The reaction was terminated by adding water, and after separation, the organic layer was washed with 0.1 N hydrochloric acid and water. The obtained solution was dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 2.7 g (64% yield) of compound S-24.

[0435] The NMR data for compound S-24 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.46 (t, OH, ¹H), 3.16 (m, CH₂, 4H), 3.68 (d, CH₂, 2H), 4.32 (s, CH₂, 2H), 6.55 (s, NH, ¹H); 7.01 (Ar, 2H), 7.13 - 7.25 (Ar, 5H), 7.40 (Ar, 2H), 7.51 (Ar, 2H), 7.59 (Ar, 1H)

[0436] Compound S-24 (2.7 g), dibenzothiophene-4-boronic acid (3.0 g), and potassium phosphate (2.9 g) were suspended in 19 mL of toluene, 19 mL of ethanol, and 10 mL of water, and degassed by purging with nitrogen. 82 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with 1 N sodium hydroxide aqueous solution. The solution was then washed with water and brine, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 3.4 g (85% yield) of compound S-25.

[0437] The NMR data for compound S-25 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 1.99 (brs, OH, ¹H), 2.67 - 2.79 (m, CH₂, 4H), 3.17 (brd, CH₂, 2H), 3.86 (brs, CH₂, 2H), 6.29 (s, NH, ¹H), 7.22 - 7.58 (Ar, 2³H), 7.70 - 7.74 (Ar, 2H), 7.80 - 7.84 (Ar, ¹H), 8.08 - 8.22 (Ar, 7H)

[0438] Compound S-25 (2.9 g) was dissolved in 30 mL of dichloromethane, and 24 mg of dibutyltin diacetate was added. 0.63 g of ethyl 2-isocyanate acrylate was added to the solution, and the reaction was carried out at room temperature for approximately 72 hours. After the reaction was complete, the solution was purified using a silicone column (dichloromethane, ethyl acetate), and the obtained fraction was concentrated to a total volume of 20 g at a temperature below 30°C. This solution was added dropwise to 350 mL of ice-cold methanol, and stirred directly for 2 hours. The precipitate was filtered, washed with methanol, and dried to obtain 2.9 g (89% yield) of compound M-10.

[0439] The NMR data of compound M-10 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 2.68 (brs, CH2, 4H), 3.00+3.22 (brs+m, CH2, 2H), 3.76 (brs, CH2, 2H), 3.82 (brs, CH2, 2H), 3.92+4.07 (brs+t, CH2, 2H), 4.48 (brt, NH, 1H), 5.80 (d, 1H), 6.11 (dd, 1H), 6.33 (s, NH, 1H), 6.39 (d, 1H), 7.19 - 7.50 (Ar, 22H), 7.53 - 7.60 (Ar, 2H), 7.71 - 7.76 (Ar, 2H), 7.80 - 7.85 (Ar, 1H), 8.08 - 8.23 ​​(Ar, 6H)

[0440] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-10 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0441] (Example 11) Compound M-11 was manufactured by the following synthesis method.

[0442] [Chemistry 32]

[0443] Under a nitrogen atmosphere, 8.0 g of pentaerythritol dibromide was dissolved in 80 ml of methyl ethyl ketone (MEK), 12.7 g of 3-bromothiophenol and 9.1 g of potassium carbonate were added, and the mixture was reacted under reflux for 4 hours. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate, washed with 1 N sodium hydroxide solution, and then washed with brine. The resulting solution was dried over anhydrous magnesium sulfate and concentrated, and then purified using a silicone column (dichloromethane, ethyl acetate) to obtain 13.0 g (87% yield) of compound S-26.

[0444] The NMR data for compound S-26 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.06 (t, OH, 2H), 3.12 (s, CH₂, 4H), 3.73 (d, CH₂, 4H), 7.12 (Ar, 2H), 7.26 - 7.32 (Ar, 4H), 7.49 (Ar, 2H)

[0445] Compound S-26 (6.0 g) was dissolved in 120 mL of dichloromethane, and 2.25 g of carbonyl diimidazole was added. After reacting at room temperature for 3 hours, water was added to terminate the reaction. After separation, the organic layer was washed with 0.1 N hydrochloric acid. Then, it was washed with brine and water, and dried with anhydrous magnesium sulfate. After concentration, the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 5.2 g (79% yield) of compound S-27.

[0446] The NMR data for compound S-27 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.19 (s, CH₂, 4H), 4.31 (s, CH₂, 4H), 7.16 (Ar, 2H), 7.27 (Ar, 2H), 7.36 (Ar, 2H), 7.48 (Ar, 2H)

[0447] Compound S-27 (1.5 g) was dissolved in 10 mL of dichloromethane, and 0.55 g of 2-phenoxyethylamine was added. After reacting at room temperature for 4 hours, the mixture was washed with water and precipitated with anhydrous magnesium sulfate. After concentration, the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 1.7 g (yield 87%) of compound S-28.

[0448] The NMR data of compound S-28 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 2.97 (t, OH, 1H), 3.00 - 3.15 (m, CH2, 4H), 3.50 (d, CH2, 2H), 3.44+3.59 (brs+q, CH2, 2H), 3.97+4.03 (brs+t, CH2, 2H), 4.14+4.23 (s+brs, CH2, 2H), 5.00+5.23 (brs+brt, NH, 1H), 6.89 (Ar, 2H), 6.98 (Ar, 1H), 7.09 (Ar, 2H), 7.26 - 7.33 (Ar, 6H), 7.49 (Ar, 2H)

[0449] Compound S-28 (1.7 g), dibenzothiophene-4-boronic acid (1.2 g), and potassium phosphate (1.1 g) were suspended in 11 mL of toluene, 11 mL of ethanol, and 5 mL of water, and degassed by purging with nitrogen. 45 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 4 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with 1 N sodium hydroxide aqueous solution. The mixture was then washed with water and brine, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 1.7 g (84% yield) of compound S-29.

[0450] The NMR data of compound S-29 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 2.92 (t, OH, 1H), 3.22 (dd, CH2, 4H), 3.28+3.45 (brs+q, CH2, 2H), 3.58 (d, CH2, 2H), 3.69+3.89 (brs+t, CH2, 2H), 4.24+4.32 (s+brs, CH2, 2H), 4.89+5.06 (brs+brt, NH, 1H), 6.70+6.76 (Ar, 2H), 6.92 (Ar, 1H), 7.21 (Ar, 2H), 7.7.33 (Ar, 2H), 7.38 - 7.53 (Ar, 12H), 7.76 (Ar, 4H), 8.12 (Ar, 4H)

[0451] Compound S-29 (1.8 g) was dissolved in 17 mL of dichloromethane, and 17 mg of dibutyltin diacetate was added. 0.46 g of ethyl 2-isocyanate acrylate was added to this solution, and the reaction was carried out at room temperature for approximately 72 hours. After the reaction was complete, the solution was purified using a silicone column (dichloromethane, ethyl acetate), and the obtained fraction was concentrated to a total volume of 10 g at a temperature below 30°C. This solution was added dropwise to 180 mL of ice-cold methanol, and stirred directly for 2 hours. The precipitate was filtered, washed with methanol, and dried to obtain 1.2 g (61% yield) of compound M-11.

[0452] The NMR data of compound M-11 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm), 3.21 - 3.35 (br, CH2, 6H), 3.41 (q, CH2, 2H), 3.77+3.86 (brs+t, CH2, 2H), 4.07 (t, CH2, 2H), 4.24 (brs, CH2, 2H), 4.80 (brt, NH, 1H), 4.67+4.99 (brs+brt, NH, 1H), 5.70 (d, 1H), 5.94 (dd, 1H), 6.30 (d, 1H), 6.72 (Ar, 2H), 6.92 (Ar, 1H), 7.18 (Ar, 2H), 7.32 (Ar, 2H), 7.38 - 7.53 (Ar, 12H), 7.75 - 7.82 (Ar, 4H), 8.12 (Ar, 4H)

[0453] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-11 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0454] (Example 12) Compound M-12 was manufactured by the following synthesis method.

[0455] [Chemical 33] Compound S-16 (1.3 g) obtained in Example 6 and 0.6 mL of diisopropylethylamine were dissolved in 10 mL of dichloromethane and cooled to 0°C. 1 mL of a solution of 300 mg acrylamide in dichloromethane was added to this solution, and the mixture was stirred for 2 hours. After the reaction was complete, 10 mL of saturated sodium bicarbonate aqueous solution was added, and the mixture was extracted twice with 50 mL of dichloromethane. The organic layer was dried with sodium sulfate, filtered, and concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 770 mg (54% yield) of compound M-12.

[0456] The NMR data of compound M-12 are shown below. 1H NMR (400 MHz, CDCl3, δ, ppm) 3.34 (d, 1H), 3.53 (d, 1H), 4.06 (d, 1H), 4.09 (d, 1H), 4.37 (d, 1H), 4.47 (d, 1H), 4.56 (d, 1H), 4.70 (d, 1H), 5.83 (dd, 1H), 6.08 (dd, 1H), 6.37 (dd, 1H), 7.22 (Ar, 4H), 7.28 (Ar, 1H), 7.37 (Ar, 3H), 7.45 (d, 1H), 7.51 (d, 1H), 7.66 (brd, 1H), 7.73 (brd, 1H), 7.80 (d, 1H), 7.87 (Ar, 2H), 7.94 (d, 1H)

[0457] (Example 13) Compound M-13 was manufactured by the following synthesis method.

[0458] [Chemical 34]

[0459] 5.1 g of 3-bromo-9H-carbazole, 2.5 g of bis(bromomethyl)oxetane, 2.9 g of potassium carbonate, and 0.1 g of benzyltrimethylammonium bromide were suspended in 5 mL of diethylene glycol dimethyl ether. The reaction mixture was heated to 120 °C and stirred for 3 hours. After cooling to room temperature, the resulting solid was filtered, washed with a mixture of ethyl acetate and hexane, and dried under reduced pressure to obtain 5.2 g of compound S-30.

[0460] The NMR data for compound S-30 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.58 (s, 4H), 4.63 (s, 4H), 7.14 (d, 2H), 7.26 (d, 2H), 7.29 (d, 2H), 7.45 (Ar, 2H), 7.50 (dd, 2H), 8.07 (d, 2H), 8.23 ​​(d, 2H)

[0461] Compound S-30 (3.5 g), dibenzothiophene-4-boronic acid (2.8 g), and potassium phosphate (5.2 g) were suspended in 60 mL of toluene, 30 mL of ethanol, and 30 mL of water, and degassed by purging with nitrogen. 31 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer, followed by stirring for 30 minutes. After filtration through diatomaceous earth, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 4.3 g (90% yield) of compound S-31.

[0462] The NMR data for compound S-31 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.77 (s, 4H), 4.81 (s, 4H), 7.32 (t, 2H), 7.38 (d, 2H), 7.47 (Ar, 8H), 7.59 (d, 4H), 7.83 (Ar, 4H), 8.19 (Ar, 6H), 8.51 (d, 2H)

[0463] Compound S-31 (4.8 g), 2-mercaptobenzothiazole (1.1 g), and toluenesulfonic acid monohydrate (106 mg) were suspended in 30 mL of toluene. The reaction solution was heated to 100 °C and stirred for 5 minutes under a nitrogen atmosphere. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 3.8 g (65% yield) of compound S-32.

[0464] The NMR data for compound S-32 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.99 (s, 2H), 4.27 (s, 2H), 4.62 (d, 2H), 4.98 (d, 2H), 7.29 (t, 2H), 7.46 (Ar, 9H), 7.58 (Ar, 7H), 7.66 (Ar, 2H), 7.80 (Ar, 2H), 7.85 (Ar, 2H), 8.19 (Ar, 6H), 8.49 (d, 2H)

[0465] Compound S-32 (3.8 g) was dissolved in 30 mL of tetrahydrofuran, and 60 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.9 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and extraction was performed using 50 mL of chloroform. The resulting organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 3.4 g (78% yield) of compound M-13.

[0466] The NMR data for compound M-13 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.32 (m, 2H), 4.11 (m, 4H), 4.55 (s, 2H), 4.61 (brt, NH, 1H), 4.82 (s, 4H), 5.74 (d, 1H), 6.08 (dd, 1H), 6.36 (d, 1H), 7.29 (t, 2H), 7.44 (Ar, 10H), 7.58 (Ar, 6H), 7.73 (Ar, 2H), 7.82 (Ar, 4H), 8.17 (Ar, 6H), 8.47 (d, 2H)

[0467] (Example 14) Compound M-14 was manufactured by the following synthesis method.

[0468] [Chemistry 35]

[0469] 10 g of bis(bromomethyl)oxetane, 16.3 g of 4-bromothiophenol, and 28 g of cesium carbonate were suspended in 150 mL of methyl ethyl ketone (MEK). The reaction mixture was heated to 90 °C, and the reaction was confirmed by LC analysis while stirring under reflux for 3 hours. After cooling the mixture to room temperature, it was extracted twice with 300 mL of water and 150 mL of ethyl acetate. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 18.1 g (94% yield) of compound S-33.

[0470] The NMR data for compound S-33 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.42 (s, 4H), 4.41 (s, 4H), 7.22 (td, 4H), 7.40 (td, 4H)

[0471] Compound S-33 (6.8 g), thiam-1-boronic acid (8.5 g), dichlorobis[triphenylphosphino]palladium(II) 1.04 g, and potassium hydroxide (8.3 g) were suspended in 360 mL of tetrahydrofuran and 90 mL of water, and degassed by purging with nitrogen. The reaction solution was heated to 80 °C and stirred for 12 hours under a nitrogen atmosphere. After cooling to room temperature, 100 mL of ethyl acetate was added, and the mixture was extracted with 200 mL of water. The organic layer was concentrated, and the crude product was purified using a silicone column (heptane-ethyl acetate) to obtain 6.4 g (59% yield) of compound S-34.

[0472] The NMR data for compound S-34 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.60 (s, 4H), 4.53 (s, 4H), 7.16 (Ar, 4H), 7.22 (Ar, 4H), 7.34 (Ar, 6H), 7.49 (Ar, 8H)

[0473] Compound S-34 (5.5 g), 2-mercaptobenzothiazole (1.5 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 30 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 1 hour. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 5.5 g (81% yield) of compound S-35.

[0474] The NMR data for compound S-35 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.26 (d, 2H), 3.46 (d, 2H), 3.68 (d, 2H), 3.70 (s, 2H), 5.58 (t, OH, 1H), 7.20 (Ar, 5H), 7.33 (Ar, 8H), 7.46 (Ar, 7H), 7.55 (d, 4H), 7.74 (brd, 1H), 7.83 (brd, 1H)

[0475] Compound S-35 (3.6 g) was dissolved in 30 mL of dichloromethane, and 28 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.63 g) was added to the solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.5 g of ethyl 2-isocyanate acrylate was added, and the reaction was carried out for another 24 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by 50 mL of chloroform for extraction. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 1.0 g (24% yield) of compound M-14.

[0476] The NMR data for compound M-14 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.39 (s, 4H), 3.84 (s, 2H), 4.17 (m, 4H), 4.32 (s, 2H), 5.00 (brt, OH, 1H), 5.80 (d, 1H), 6.12 (dd, 1H), 6.40 (d, 1H), 7.13 (Ar, 4H), 7.21 (Ar, 5H), 7.28 (Ar, 8H), 7.40 (Ar, 1H), 7.48 (d, 6H), 7.71 (brd, 1H), 7.87 (brd, 1H)

[0477] (Example 15) Compound M-15 was manufactured by the following synthesis method.

[0478] [Chemistry 36]

[0479] Dissolve 6.7 g of o-vanillin and 5.0 g of 2-aminobenzylthiol in 10 mL of ethanol. Stir the reaction mixture under reflux for 5 hours. After cooling to room temperature, stir at room temperature under atmospheric pressure for 48 hours. Concentrate the reaction mixture, filter the resulting solid, wash with 2-butanone, and dry under reduced pressure to give 5.4 g (53% yield) of compound S-36.

[0480] The NMR data for compound S-36 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.95 (s, 6H), 6.90 (dd, 1H), 6.99 (dd, 1H), 7.32 (dd, 1H), 7.41 (ddd, 1H), 7.51 (ddd, 1H), 7.90 (d, 1H), 8.01 (d, 1H), 12.74 (brs, HO, 1H)

[0481] Compound S-36 (4.2 g), bis(bromomethyl)oxetane (2.0 g), and potassium carbonate (2.3 g) were dissolved in 10 mL of dimethylformamide (DMF). The reaction mixture was heated to 120 °C and stirred for 2 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture for extraction. The organic layer was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to give 2.9 g (59% yield) of compound S-37.

[0482] The NMR data for compound S-37 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.85 (s, 6H), 4.59 (s, 4H), 4.97 (s, 4H), 7.04 (dd, 2H), 7.20 (dd, 2H), 7.34 (ddd, 2H), 7.45 (ddd, 2H), 7.81 (d, 2H), 7.96 (dd, 2H), 8.05 (d, 2H)

[0483] Compound S-37 (2.9 g), 2-mercaptobenzothiazole (0.82 g), and toluenesulfonic acid monohydrate (50 mg) were suspended in 10 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 3 hours. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 3.5 g (94% yield) of compound S-38.

[0484] The NMR data for compound S-38 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.85 (s, 6H) 4.18 (s, 2H), 4.22 (s, 2H), 4.43 (d, 2H), 4.45 (d, 2H), 4.66 (brs, 1H), 7.01 (dd, 2H), 7.19 (dd, 2H), 7.29 (Ar, 3H), 7.40 (Ar, 3H), 7.71 (d, 2H), 7.72 (d, 1H), 7.78 (dd, 2H), 7.80 (d, 1H), 8.05 (d, 2H)

[0485] Compound S-38 (3.5 g) was dissolved in 10 mL of tetrahydrofuran, and 38 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.65 g) was added to the solution, and the reaction was carried out at room temperature. After 48 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with 50 mL of chloroform. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 1.3 g (32% yield) of compound M-15.

[0486] The NMR data for compound M-15 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.32 (m, 2H), 3.85 (s, 6H), 4.06 (m, 2H), 4.23 (s, 2H), 4.41 (m, 4H), 4.79 (brt, 1H), 4.84 (s, 2H), 5.77 (d, 1H), 6.02 (dd, 1H), 6.35 (d, 1H), 7.00 (dd, 2H), 7.18 (dd, 2H), 7.30 (Ar, 3H), 7.40 (Ar, 3H), 7.76 (Ar, 4H), 7.86 (dd, 2H), 8.03 (d, 2H)

[0487] (Example 16) Compound M-16 was manufactured by the following synthesis method.

[0488] [Chemistry 37]

[0489] 3.7 g of 5-bromovanillin and 2.0 g of 2-aminobenzylthiol were dissolved in 10 mL of ethanol. The reaction mixture was stirred under reflux for 5 hours. After cooling to room temperature, it was stirred at room temperature under atmospheric pressure for 72 hours. The reaction mixture was concentrated, and the resulting solid was separated by filtration, washed with 2-butanone, and dried under reduced pressure to give 3.5 g (65% yield) of compound S-39.

[0490] The NMR data for compound S-39 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.40 (s, 3H), 6.23 (s, OH, 1H), 7.38 (dd, 1H), 7.49 (dd, 1H), 7.65 (d, 1H), 7.80 (d, 1H), 7.89 (d, 1H), 8.04 (d, 1H)

[0491] Compound S-39 (3.3 g), bis(bromomethyl)oxetane (1.2 g), and potassium carbonate (1.4 g) were dissolved in 10 mL of dimethylformamide (DMF). The reaction mixture was heated to 120 °C and stirred for 2 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture, and extraction was performed. The organic layer was concentrated to obtain 3.7 g of crude product S-40.

[0492] The NMR data for compound S-40 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.99 (s, 6H), 4.57 (s, 4H), 4.86 (s, 4H), 7.39 (dd, 2H), 7.50 (dd, 2H), 7.66 (s, 2H), 7.81 (s, 2H), 7.89 (d, 2H), 8.04 (d, 2H)

[0493] Compound S-40 (3.7 g), dibenzothiophene-4-boronic acid (2.5 g), and potassium phosphate (3.2 g) were suspended in 60 mL of dimethyl ether and 10 mL of water, and degassed by purging with nitrogen. 81 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer, followed by stirring for 30 minutes. After filtration through diatomaceous earth, the solution was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 4.7 g of crude compound S-41.

[0494] The NMR data for compound S-41 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.56 (s, 4H), 3.84 (s, 6H), 3.96 (s, 4H), 7.22 (Ar, 2H), 7.39 (Ar, 8H), 7.51 (Ar, 2H), 7.72 (Ar, 6H), 7.91 (d, 2H), 8.01 (dd, 2H), 8.09 (Ar, 4H)

[0495] Compound S-41 (4.7 g), 2-mercaptobenzothiazole (0.90 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 10 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 3 hours. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product obtained was purified using a silicone column (hexane / ethyl acetate) to give 5.5 g of compound S-42.

[0496] The NMR data for compound S-42 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.96 (s, 2H), 3.22 (d, 2H), 3.46 (s, 4H), 3.53 (brt, OH, 1H), 3.81 (s, 6H), 7.20 (Ar, 2H), 7.24 (dd, 1H), 7.36 (Ar, 9H), 7.51 (ddd, 2H), 7.58 (d, 1H), 7.64 (Ar, 3H), 7.69 (Ar, 4H), 7.90 (d, 2H), 7.97 (dd, 2H), 8.02 (Ar, 2H), 8.09 (d, 2H)

[0497] Compound S-42 (5.5 g) was dissolved in 10 mL of tetrahydrofuran, and 34 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.83 g) was added to the solution, and the reaction was carried out at room temperature. After 48 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with 50 mL of chloroform. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 2.8 g (45% yield) of compound M-16.

[0498] The NMR data of compound M-16 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 3.14 (m, 4H), 3.45 (s, 4H), 3.79 (s, 6H), 3.88 (s, 2H), 4.03 (brt, 2H), 4.40 (t, NH, 1H), 5.82 (d, 1H), 6.09 (dd, 1H), 6.40 (d, 1H), 7.22 (Ar, 3H), 7.37 (Ar, 9H), 7.50 (ddd, 2H), 7.56 (d, 1H), 7.66 (Ar, 5H), 7.72 (Ar, 2H), 7.90 (d, 2H), 7.95 (dd, 2H), 8.02 (Ar, 2H), 8.08 (d, 2H)

[0499] (Example 17) Compound M-17 was manufactured by the following synthesis method.

[0500] [Chemistry 38]

[0501] 2,4-Dibromophenol (2.3 g), bis(bromomethyl)oxetane (1.0 g), and cesium carbonate (2.7 g) were dissolved in 5 mL of 1-methyl-2-pyrrolidone (NMP). The reaction mixture was heated to 130 °C and stirred for 2 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture for extraction. The organic layer was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to give 1.9 g (79% yield) of compound S-43.

[0502] The NMR data for compound S-43 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.41 (s, 4H), 4.71 (s, 4H), 6.85 (d, 2H), 7.38 (dd, 2H), 7.65 (d, 2H)

[0503] Compound S-43 (8.9 g), dibenzothiophene-4-boronic acid (15 g), and potassium phosphate (19.3 g) were suspended in 150 mL of tetrahydrofuran and 30 mL of water, and degassed by purging with nitrogen. 181 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After filtration through diatomaceous earth, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 15 g of crude compound S-44.

[0504] The NMR data for compound S-44 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.98 (s, 4H), 4.15 (s, 4H), 6.75 (d, 2H), 7.36 (dd, 2H), 7.52 (Ar, 16H), 7.71 (Ar, 2H), 7.85 (Ar, 4H), 8.17 (Ar, 8H)

[0505] The crude product of compound S-44 (5.0 g), 2-mercaptobenzothiazole (0.90 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 70 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling the mixture to room temperature, 20 mL of tetrahydrofuran was added to prepare a homogeneous solution, which was washed with 1 M sodium hydroxide aqueous solution. Subsequently, the solution was washed with 0.1 N hydrochloric acid and water, and the organic layer was dried and concentrated with anhydrous magnesium sulfate. The obtained crude product was dissolved in 20 mL of dichloromethane and slowly added dropwise to 150 mL of acetonitrile while stirring. After stirring for another 2 hours, the precipitate was separated by filtration. The obtained solid was dissolved again in 80 mL of dichloromethane, passed through a silicone short-pass column, and concentrated to obtain 3.8 g (73% yield) of compound S-45.

[0506] The NMR data for compound S-45 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.03 (s, 2H), 3.22 (d, 2H), 3.61 (d, 2H), 3.81 (d, 2H), 4.69 (brt, OH, 1H), 6.67 (d, 2H), 4.15 (s, 4H), 6.75 (d, 2H), 7.28 (Ar, 3H), 7.39 (Ar, 3H), 7.52 (Ar, 13H), 7.67 (Ar, 3H), 7.83 (Ar, 4H), 8.17 (Ar, 8H)

[0507] Compound S-45 (3.5 g) was dissolved in 35 mL of dichloromethane, and 24 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.68 g) was added to the solution, and the reaction was carried out at room temperature for 50 hours. After the reaction was completed, the reaction solution was concentrated at a temperature below 30°C, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 3.0 g (80% yield) of compound M-17.

[0508] The NMR data of compound M-17 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 3.21 (m, 4H), 3.83 (s, 4H), 3.87 (s, 2H), 4.06 (m, 2H), 4.59 (brt, NH, 1H), 5.81 (d, 1H), 6.08 (dd, 1H), 6.39 (d, 1H), 6.62 (d, 2H), 7.24 (Ar, 1H), 7.32 (Ar, 3H), 7.39 (Ar, 2H), 7.39 (Ar, 3H), 7.48 (Ar, 11H), 7.55 (Ar, 2H), 7.62 (Ar, 2H), 7.69 (Ar, 2H), 7.82 (Ar, 2H), 7.85 (Ar, 2H), 8.17 (Ar, 8H)

[0509] (Example 18) Compound M-18 was manufactured by the following synthesis method.

[0510] [Chemistry 39]

[0511] Compound S-44 (20 g), obtained in Example 17, 5-methyl-1,3,4-thiadiazole-2-thiol (3.2 g), and toluenesulfonic acid monohydrate (200 mg) were suspended in 150 mL of toluene. The reaction solution was heated to 120°C under a nitrogen atmosphere and stirred under reflux for 7 hours. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 15.5 g (68% yield) of compound S-46.

[0512] The NMR data for compound S-46 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.62 (s, 3H), 2.99 (s, 2H), 3.22 (d, 2H), 3.62 (d, 2H), 3.82 (d, 2H), 3.85 (brt, OH, 1H), 6.67 (d, 2H), 7.30 (dd, 2H), 7.48 (Ar, 16H), 7.68 (Ar, 2H), 7.81 (Ar, 2H), 7.85 (Ar, 2H), 8.18 (Ar, 8H)

[0513] Compound S-46 (3.2 g) was dissolved in 10 mL of tetrahydrofuran, and 20 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.60 g) was added to the solution, and the reaction was carried out at room temperature. After 48 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with 50 mL of chloroform. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 1.3 g (36% yield) of compound M-18.

[0514] The NMR data of compound M-18 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm) 2.56 (s, 3H), 3.11 (s, 2H), 3.30 (m, 2H), 3.75 (m, 4H), 3.82 (s, 2H), 3.84 (s, 2H), 4.68 (brt, NH, 1H), 5.81 (d, 1H), 6.11 (dd, 1H), 6.40 (d, 1H), 6.62 (d, 2H), 7.36 (Ar, 2H), 7.49 (Ar, 16H), 7.73 (Ar, 2H), 7.82 (Ar, 2H), 7.86 (Ar, 2H), 8.18 (Ar, 8H)

[0515] (Example 19) Compound M-19 was manufactured by the following synthesis method.

[0516] [Chemistry 40]

[0517] 10 g of 3,6-dibromo-9H-carbazole, 14.7 g of dibenzothiophene-4-boronic acid, and 19.6 g of potassium phosphate were suspended in 100 mL of toluene, 100 mL of ethanol, and 50 mL of water, and degassed by purging with nitrogen. 11 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was then purged for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, the resulting solid was filtered and washed with ethanol to obtain 15 g (92% yield) of compound S-47.

[0518] The NMR data for compound S-47 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 7.46 (Ar, 4H), 7.60 (Ar, 6H), 7.84 (Ar, 4H), 8.18 (dd, 4H), 8.50 (s, 2H)

[0519] Compound S-47 (4.4 g), bis(bromomethyl)oxetane (1.0 g), sodium hydroxide (0.41 g), and benzyltrimethylammonium bromide (21 mg) were suspended in 10 mL of diethylene glycol dimethyl ether. The reaction mixture was heated to 150 °C and stirred for 3 hours. After cooling to room temperature, the resulting solid was filtered and washed with acetone to obtain 3.3 g (70% yield) of compound S-48.

[0520] The NMR data for compound S-48 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.89 (m, 8H), 7.44 (Ar, 8H), 7.58 (Ar, 12H), 7.79 (Ar, 4H), 7.92 (Ar, 4H), 8.18 (Ar, 8H), 8.57 (Ar, 4H)

[0521] Compound S-48 (1.0 g), 5-methyl-1,3,4-thiadiazole-2-thiol (0.18 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 10 mL of xylene. The reaction solution was heated to 150 °C under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 0.92 g (83% yield) of compound S-49.

[0522] The NMR data for compound S-49 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 1.53 (s, 3H), 4.01 (m, 4H), 4.81 (d, 2H), 4.93 (d, 2H), 7.40 (Ar, 4H), 7.46 (Ar, 4H), 7.58 (Ar, 8H), 7.74 (Ar, 8H), 7.90 (Ar, 4H), 8.17 (Ar, 8H), 8.53 (Ar, 4H)

[0523] Compound S-49 (2.2 g) was dissolved in 10 mL of tetrahydrofuran, and 34 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.37 g) was added to the solution, and the reaction was carried out at room temperature. After 72 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with 50 mL of chloroform. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 1.3 g (53% yield) of compound M-19.

[0524] The NMR data for compound M-19 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 1.53 (s, 3H), 3.48 (m, 2H), 3.95 (s, 2H), 4.24 (m, 2H), 4.56 (s, 2H), 4.71 (d, 2H), 4.95 (m, 3H), 5.68 (d, 1H), 6.05 (dd, 1H), 6.33 (d, 1H), 7.43 (Ar, 8H), 7.58 (Ar, 12H), 7.75 (Ar, 4H), 7.90 (Ar, 4H), 8.16 (Ar, 8H), 8.53 (Ar, 4H)

[0525] (Example 20) Compound M-20 was manufactured by the following synthesis method.

[0526] [Chemistry 41]

[0527] Compound S-11 (3.5 g), 5-methyl-1,3,4-thiadiazole-2-thiol (0.84 g), and toluenesulfonic acid monohydrate (100 mg) obtained in Example 4 were suspended in 10 mL of toluene. The reaction solution was heated to 120°C under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, toluenesulfonic acid monohydrate (100 mg) was added, and the mixture was stirred under reflux for 3 hours. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product obtained was purified using a silicone column (hexane / ethyl acetate) to obtain 3.1 g (74% yield) of compound S-50.

[0528] The NMR data for compound S-50 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.67 (s, 3H), 3.20 (d, 2H), 3.42 (d, 2H), 3.62 (d, 2H), 3.64 (s, 2H), 4.74 (t, OH, 1H), 7.35 (Ar, 2H), 7.45 (Ar, 12H), 7.76 (Ar, 4H), 8.09 (dd, 2H), 8.15 (dd, 2H)

[0529] Compound S-50 (3.1 g) was dissolved in 10 mL of tetrahydrofuran, and 27 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.82 g) was added to the solution, and the reaction was carried out at room temperature. After 72 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and extraction was performed using 150 mL of ethyl acetate. The resulting organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 1.3 g (36% yield) of compound M-20.

[0530] The NMR data for compound M-20 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.60 (s, 3H), 3.29 (m, 2H), 3.34 (m, 4H), 3.79 (s, 2H), 4.08 (t, 2H), 4.26 (s, 2H), 4.86 (brs, NH, 1H), 5.71 (d, 1H), 5.95 (dd, 1H), 6.31 (d, 1H), 7.33 (Ar, 2H), 7.45 (Ar, 12H), 7.74 (Ar, 2H), 7.79 (Ar, 2H), 8.10 (d, 2H), 8.14 (d, 2H)

[0531] (Example 21) Compound M-21 was manufactured by the following synthesis method.

[0532] [Chemical 42]

[0533] Compound S-11 (5.0 g), 5-chloro-2-mercaptobenzothiazole (1.81 g), and toluenesulfonic acid monohydrate (100 mg) obtained in Example 4 were suspended in 20 mL of toluene. The reaction solution was heated to 120 °C under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product obtained was purified using a silicone column (hexane / ethyl acetate) to give 4.4 g (68% yield) of compound S-51.

[0534] The NMR data for compound S-51 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.23 (d, 2H), 3.43 (d, 2H), 3.63 (d, 2H), 3.68 (s, 2H), 5.05 (t, OH, 1H), 7.43 (Ar, 15H), 7.59 (d, 1H), 7.76 (Ar, 5H), 8.10 (dd, 2H), 8.15 (dd, 2H)

[0535] Compound S-51 (4.4 g) was dissolved in 10 mL of tetrahydrofuran, and 36 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.93 g) was added to the solution, and the reaction was carried out at room temperature. After 72 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and extraction was performed using 150 mL of ethyl acetate. The resulting organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 1.9 g (37% yield) of compound M-21.

[0536] The NMR data for compound M-21 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.24 (brdd, 2H), 3.38 (s, 4H), 3.82 (s, 2H), 4.04 (t, 2H), 4.29 (s, 2H), 4.79 (brt, NH, 1H), 5.70 (d, 1H), 5.93 (dd, 1H), 6.30 (d, 1H), 7.15 (dd, 1H), 7.33 (dd, 2H), 7.44 (Ar, 13H), 7.75 (Ar, 5H), 8.11 (dd, 2H), 8.15 (Ar, 2H)

[0537] (Example 22) Compound M-22 was manufactured by the following synthesis method.

[0538] [Chemistry 43]

[0539] 2.6 g of 7H-dibenzo[c,g]carbazole, 1.2 g of bis(bromomethyl)oxetane, 0.66 g of sodium hydroxide, and 20 mg of benzyltrimethylammonium bromide were suspended in 5 mL of diethylene glycol dimethyl ether. The reaction mixture was heated to 120 °C and stirred for 3 hours. After cooling to room temperature, the resulting white solid was filtered, washed with methanol, and dried under reduced pressure to obtain 1.6 g (53% yield) of compound S-52.

[0540] The NMR data for compound S-52 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 4.60 (s, 4H), 5.00 (s, 4H), 7.53 (Ar, 4H), 7.55 (Ar, 4H), 7.70 (Ar, 4H), 7.85 (d, 4H), 8.02 (d, 4H), 9.22 (d, 4H)

[0541] Compound S-52 (1.0 g), 2-mercaptobenzothiazole (0.28 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 30 mL of toluene. The reaction solution was heated to 100 °C and stirred for 5 minutes under a nitrogen atmosphere. After cooling the mixture to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using a silicone column (hexane / ethyl acetate) to give 0.9 g (71% yield) of compound S-53.

[0542] The NMR data for compound S-53 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.35 (s, 2H), 3.79 (s, 2H), 4.70 (d, 2H), 5.08 (d, 2H), 5.09 (brs, OH, 1H), 7.23 (Ar, 1H), 7.35 (t, 1H), 7.51 (Ar, 5H), 7.69 (Ar, 9H), 7.80 (d, 4H), 7.98 (d, 4H), 9.20 (d, 4H)

[0543] Compound S-53 (1.7 g) was dissolved in 30 mL of tetrahydrofuran, and 55 mg of dibutyltin diacetate was added. Ethyl 2-isocyanate acrylate (0.5 g) was added to the solution, and the reaction was carried out at room temperature. After 48 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with 50 mL of chloroform. The resulting organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 1.1 g (55% yield) of compound M-22.

[0544] The NMR data for compound M-22 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.93 (m, 2H), 3.78 (s, 2H), 3.82 (m, 2H), 4.26 (s, 2H), 4.30 (brt, OH, 1H), 4.74 (s, 4H), 5.70 (d, 1H), 5.96 (dd, 1H), 6.29 (d, 1H), 7.19 (t, 1H), 7.29 (t, 1H), 7.47 (Ar, 8H), 7.60 (Ar, 6H), 7.69 (Ar, 4H), 7.90 (d, 4H), 9.11 (d, 4H)

[0545] (Example 23) Compound M-23 was manufactured by the following synthesis method.

[0546] [Chemistry 44]

[0547] Compound S-27 (2.0 g) obtained in Example 11 was dissolved in 10 mL of dichloromethane under a nitrogen atmosphere, and 1.2 g of 2-(3-bromophenoxy)ethylamine was added. After reacting at room temperature for 3 hours, 0.3 g of 2-(3-bromophenoxy)ethylamine was added, and the reaction was carried out under reflux for 1 hour. The resulting solution was washed with water and dried with anhydrous magnesium sulfate. After concentration, the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 2.5 g (yield 84%) of compound S-54.

[0548] The NMR data for compound S-54 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.90 (t, OH, ¹H), 3.01 - 3.15 (m, CH₂, 4H), 3.50 (d, CH₂, 2H), 3.45+3.58 (brs+q, CH₂, 2H), 3.95+4.01 (brs+t, CH₂, 2H), 4.14+4.23 (s+brs, CH₂, 2H), 4.97+5.18 (brs+brt, NH, ¹H), 6.82 (Ar, ¹H), 7.00 - 7.18 (Ar, 5H), 7.27 (Ar, 4H), 7.50 (Ar, 2H)

[0549] Compound S-54 (2.5 g), dibenzothiophene-4-boronic acid (2.2 g), and potassium phosphate (2.2 g) were suspended in 16 mL of toluene, 16 mL of ethanol, and 8 mL of water, and degassed by purging with nitrogen. 62 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was then purged for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with 1 N sodium hydroxide aqueous solution. It was then washed with water and brine, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified using a silicone column (dichloromethane, ethyl acetate) to obtain 2.5 g (75% yield) of compound S-55. The NMR data for compound S-55 are shown below. 1H NMR (400 MHz, CDCl3, δ, ppm) 2.86+3.01 (t+brs, OH, 1H), 3.23 (dd, CH2, 4H), 3.28+3.49 (brs+q, CH2, 2H), 3.60 (d, CH2, 2H), 3.79+3.98 (brs+t, CH2, 2H), 4.26+4.32 (s+brs, CH2, 2H), 4.92+5.09 (brs+t, NH, 1H), 6.75+6.86 (Ar, 1H), 7.09 - 7.18 (Ar, 1H), 7.28 - 7.56 (Ar, 20H), 7.72 - 7.83 (Ar, 5H), 8.04 - 8.21 (Ar, 6H)

[0551] Compound S-55 (2.5 g) was dissolved in 24 mL of dichloromethane, and 19 mg of dibutyltin diacetate was added. 0.51 g of ethyl 2-isocyanate acrylate was added to this solution, and the reaction was carried out at room temperature for approximately 150 hours. After the reaction was complete, the solution was purified using a silicone column (dichloromethane, ethyl acetate), and the obtained fraction was concentrated to a total volume of 13 g at a temperature below 30°C. This solution was added dropwise to 160 mL of ice-cold methanol, and stirred directly for 2 hours. The precipitate was filtered, washed with methanol, and dried to obtain 1.9 g (71% yield) of compound M-23.

[0552] The NMR data of compound M-23 are shown below. 1H NMR(400 MHz, CDCl3, δ, ppm), 3.23 - 3.34 (br, CH2, 6H), 3.44 (q, CH2, 2H), 3.85+3.93 (brs+t, CH2, 2H), 4.06 (t, CH2, 2H), 4.24 (brs, CH2, 4H), 4.80 (t, NH, 1H), 4.63+5.02 (brs+t, NH, 1H), 5.69 (d, 1H), 5.93 (dd, 1H), 6.29 (dd, 1H), 6.78 (Ar, 1H), 7.10 (Ar, 1H), 7.26 - 7.55 (Ar, 20H), 7.73 - 7.85 (Ar, 5H), 8.04 - 8.20 (Ar, 6H)

[0553] (Comparative Example 1) Compound M-24 was manufactured by the following synthetic method.

[0554] [Chemical 45]

[0555] 20 g of compound S-2 obtained in Synthesis Example 1 and 50 g of cesium carbonate were dissolved in 200 mL of methyl ethyl ketone (MEK). 9 g of pentaerythritol tribromide was added to the solution, and the mixture was heated to 90°C. The reaction was confirmed by LC analysis while stirring for 5 hours. Water was added to the reaction solution, followed by 100 mL of ethyl acetate, and the organic layer was extracted. The obtained organic layer was extracted twice with 50 mL of water, and the resulting aqueous layer was back-extracted twice with 100 mL of ethyl acetate. The obtained organic layer was dried over Glauber's salt and then concentrated. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 10 g (49% yield) of compound S-56.

[0556] The NMR data for compound S-56 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.38 (s, 6H), 3.75 (d, 2H), 7.22 (dd, 3H), 7.43 (Ar, 9H), 7.77 (Ar, 3H), 7.86 (dd, 3H), 8.02 (Ar, 3H)

[0557] Compound S-56 (11 g) was dissolved in 55 mL of tetrahydrofuran (THF), and 190 mg of dibutyltin dilaurate was added. 2.55 g of ethyl 2-isocyanate (manufactured by Showa Denko Co., Ltd., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.4 g of ethyl 2-isocyanate was added, and the reaction was carried out for another 24 hours. 100 mL of ethyl acetate was added to the reaction solution, and the mixture was concentrated to approximately 50 mL. After removing insoluble matter, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 7.6 g (58% yield) of compound M-24.

[0558] The NMR data for compound M-24 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.19 (dt, 2H), 3.36 (s, 6H), 4.02 (m, 2H), 4.21 (s, 2H), 4.42 (m, 2H), 5.79 (dd, 1H), 6.03 (dd, 1H), 6.37 (d, 1H), 7.19 (Ar, 3H), 7.38 (Ar, 3H), 7.43 (Ar, 6H), 7.76 (Ar, 3H), 7.84 (Ar, 3H), 8.01 (Ar, 3H)

[0559] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-24 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0560] (Comparative Example 2) Compound M-25 was manufactured by the following synthetic method.

[0561] [Chemistry 46]

[0562] 13.60 g of 2-bromothiophenol, 7.08 g of pentaerythritol tribromide, and 9.04 g of potassium carbonate were suspended in 21 mL of N,N-dimethylformamide (DMF). The reaction mixture was heated to 100°C, and the reaction was confirmed by LC analysis while stirring for 4 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and washed with water. The aqueous layer was back-extracted twice with ethyl acetate. The resulting organic layer was dried over sodium sulfate and concentrated. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 13.2 g (93% yield) of compound S-57.

[0563] The NMR data for compound S-57 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.23 (s, 6H), 3.79 (d, 2H), 6.98 (Ar, 3H), 7.19 (Ar, 3H), 7.33 (Ar, 3H), 7.47 (Ar, 3H)

[0564] Compound S-57 (2.0 g), dibenzothiophene-4-boronic acid (3.5 g), and potassium carbonate (2.5 g) were suspended in 20 mL of THF and 2.0 mL of water, and degassed by purging with nitrogen. Dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) (30 mg) was added to the reaction solution, and nitrogen was then purged for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After filtration through diatomaceous earth, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 2.9 g (98% yield) of compound S-58.

[0565] The NMR data for compound S-58 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.62 (s, 6H), 3.00 (d, 2H), 7.16 (Ar, 12H), 7.41 (Ar, 12H), 7.70 (Ar, 3H), 8.08 (Ar, 3H), 8.15 (Ar, 3H)

[0566] Compound S-58 (2.9 g) was dissolved in 15 mL of tetrahydrofuran (THF), and 40 mg of dibutyltin dilaurate was added. 510 mg of ethyl 2-isocyanate (manufactured by Showa Denko Co., Ltd., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 500 mg of ethyl 2-isocyanate was added, and the reaction was carried out for another 24 hours. Water was added to the reaction solution, followed by 50 mL of ethyl acetate, and the organic layer was extracted. The obtained organic layer was extracted twice with 30 mL of water, and the resulting aqueous layer was back-extracted twice with 50 mL of ethyl acetate. The obtained organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 1.5 g (yield 45%) of compound M-25.

[0567] The NMR data for compound M-25 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 2.53 (s, 6H), 3.07 (m, 2H), 3.53 (s, 2H), 3.99 (t, 2H), 4.14 (dd, 1H), 5.81 (d, 1H), 6.10 (dd, 1H), 6.40 (d, 1H), 7.11 (Ar, 12H), 7.24 (Ar, 3H), 7.36 (Ar, 3H), 7.43 (Ar, 6H), 7.71 (Ar, 3H), 8.08 (Ar, 3H), 8.16 (Ar, 3H)

[0568] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-25 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0569] (Comparative Example 3) Compound M-26 was manufactured by the following synthetic method.

[0570] [Chemistry 47]

[0571] Compound S-57 (2.0 g) obtained in Comparative Example 2, 2.7 g of thiam-1-boronic acid, and 2.5 g of potassium carbonate were suspended in 20 mL of THF and 2.0 mL of water, and degassed by purging with nitrogen. 30 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was purged for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After filtration through diatomaceous earth, the mixture was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 2.2 g (68% yield) of compound S-59.

[0572] The NMR data for compound S-59 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.57 (m, 6H), 2.98 (d, 2H), 6.99 (Ar, 6H), 7.07 (Ar, 3H), 7.14 (Ar, 12H), 7.22 (Ar, 6H), 7.44 (Ar, 6H)

[0573] Compound S-59 (1.1 g) was dissolved in 7.5 mL of tetrahydrofuran (THF), and 10 mg of dibutyltin dilaurate was added. 290 mg of ethyl 2-isocyanate (manufactured by Showa Denko Co., Ltd., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 300 mg of ethyl 2-isocyanate was added, and the reaction was carried out for another 24 hours. Water was added to the reaction solution, followed by 50 mL of ethyl acetate, and the organic layer was extracted. The obtained organic layer was extracted twice with 30 mL of water, and the resulting aqueous layer was back-extracted twice with 50 mL of ethyl acetate. The obtained organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 600 mg (50% yield) of compound M-26.

[0574] The NMR data for compound M-26 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 2.49 (m, 6H), 3.23 (m, 2H), 3.53 (s, 2H), 4.08 (t, 2H), 4.52 (dd, 1H), 5.82 (d, 1H), 6.08 (dd, 1H), 6.40 (d, 1H), 7.10 (Ar, 27H), 7.44 (Ar, 6H)

[0575] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-26 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0576] (Comparative Example 4) Compound M-27 was manufactured by the following synthetic method.

[0577] [Chemistry 48]

[0578] 4.80 g of 3-bromothiophenol, 2.50 g of pentaerythritol tribromide, and 3.19 g of potassium carbonate were suspended in 13 mL of N,N-dimethylformamide (DMF). The reaction mixture was heated to 100 °C, and the reaction was confirmed by LC analysis while stirring for 4 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and washed with water. The aqueous layer was back-extracted twice with ethyl acetate. The resulting organic layer was dried with sodium sulfate and then concentrated. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to give 5.0 g (100% yield) of compound S-60.

[0579] The NMR data for compound S-60 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.15 (s, 6H), 3.66 (d, 2H), 7.09 (Ar, 3H), 7.25 (Ar, 6H), 7.45 (Ar, 3H)

[0580] Compound S-60 (2.3 g), dibenzothiophene-4-boronic acid (3.2 g), and potassium carbonate (2.9 g) were suspended in 23 mL of THF and 3 mL of water, and degassed by purging with nitrogen. 70 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, followed by purging with nitrogen for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 6 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.5 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After filtration through diatomaceous earth, the solution was concentrated, and the crude product was purified using a silicone column (hexane / ethyl acetate) to obtain 2.9 g (87% yield) of compound S-61.

[0581] The NMR data for compound S-61 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm): 3.37 (s, 6H), 3.82 (d, 2H), 7.28 (Ar, 3H), 7.34 (Ar, 3H), 7.41 (Ar, 15H), 7.71 (Ar, 6H), 8.05 (Ar, 3H), 8.11 (Ar, 3H)

[0582] Compound S-61 (2.9 g) was dissolved in 14.5 mL of tetrahydrofuran (THF), and 40 mg of dibutyltin dilaurate was added. 850 mg of ethyl 2-isocyanate (manufactured by Showa Denko Co., Ltd., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 400 mg of ethyl 2-isocyanate was added, and the reaction was carried out for another 24 hours. Water was added to the reaction solution, followed by 100 mL of ethyl acetate, and the organic layer was extracted. The obtained organic layer was extracted twice with 50 mL of water, and the resulting aqueous layer was back-extracted twice with 50 mL of ethyl acetate. The obtained organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silicone column (hexane / ethyl acetate) to obtain 1.1 g (33% yield) of compound M-27.

[0583] The NMR data for compound M-27 are shown below. ¹H NMR (400 MHz, CDCl₃, δ, ppm) 3.22 (m, 2H), 3.37 (s, 6H), 3.99 (t, 2H), 4.30 (s, 2H), 4.70 (dd, 1H), 5.62 (d, 1H), 5.82 (dd, 1H), 6.23 (d, 1H), 7.27 (Ar, 3H), 7.38 (Ar, 18H), 7.71 (Ar, 6H), 8.05 (Ar, 3H), 8.11 (Ar, 3H)

[0584] Holographic recording media were prepared in the same manner as in Example 1, except that compound M-27 was used as the polymerizable monomer, and were evaluated. The results are shown in Table 1 below.

[0585] [Table 1] Aggregation monomer Multiplicity Total ∆n Transmittance % before recording Transmittance % after recording Haze% Haze % / Total ∆n Example 1 M-1 151 0.0172 66 86 0.05 2.91 Example 2 M-2 151 0.0199 66 85 0.04 2.01 Example 3 M-3 151 0.0216 66 85 0.06 2.78 Example 4 M-4 151 0.0213 67 84 0.05 2.35 Example 5 M-5 151 0.0217 67 85 0.05 2.30 Example 6 M-6 151 0.0129 67 84 0.04 3.10 Example 7 M-7 151 0.0157 67 84 0.04 2.55 Example 8 M-8 151 0.0205 66 86 0.07 3.41 Example 9 M-9 151 0.0208 67 83 0.07 3.37 Example 10 M-10 151 0.0214 66 84 0.07 3.27 Example 11 M-11 151 0.0138 67 88 0.04 2.90 Comparative Example 1 M-24 151 0.0190 67 85 0.07 3.68 Comparative Example 2 M-25 151 0.0194 69 87 0.07 3.61 Comparative Example 3 M-26 151 0.0220 67 85 0.09 4.09 Comparative Example 4 M-27 151 0.0214 66 82 0.09 4.21

[0586] When manufacturing holographic recording media, the molar concentrations of polymerizable monomers, photopolymerization initiators, and additives were set to inherent values. Holographic recording media were manufactured by changing only the type of polymerizable monomer, and the results were evaluated (Table 1). As shown in Table 1, in Comparative Examples 1 to 4, where the polymerizable monomers used had three high-refractive-index regions with the same structure, the haze % / total Δn was 3.6 or higher. In contrast, in Examples 1 to 11, where one high-refractive-index region was replaced with a polymerizable monomer of a different structure, the haze % / total Δn was reduced to 3.5 or lower, resulting in holographic recording media with lower haze compared to the same total Δn.

[0587] In the application of optical elements in AR glasses light guide plates, a higher total Δn of the holographic recording medium results in a brighter projected image and a wider viewing angle. Furthermore, in memory applications, an increase in total Δn can increase recording capacity. On the other hand, holographic recording media with high haze, especially in AR glasses waveguide plate applications, can cause waveguide light scattering, thus reducing light utilization efficiency and aesthetics. Therefore, by using the compound of the present invention, which balances high total Δn and low haze, it is possible to produce an AR glasses light guide plate with excellent light utilization efficiency and aesthetics. Based on the above, the compound of the present invention used in the embodiments is superior to the compound of the comparative examples.

[0588] [Refractive Index] The refractive index of the polymerizable monomers manufactured in the Examples and Comparative Examples was determined using the following method. The results are shown in Table 2. Test solutions were prepared by dissolving the sample at a predetermined concentration in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate at a mass ratio of 4:1. The test solutions were prepared with sample concentrations of 10% by mass and 20% by mass. The refractive index of each test solution was measured using a Kalnew precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-2000). The temperature of the test solution was set to 23°C, and the measurement wavelength was set to helium lamp d-rays (587.6 nm). Based on the measurement results, a calibration curve showing the correlation between sample concentration and refractive index was generated. The refractive index at a sample concentration of 100% by mass was determined from the obtained calibration curve and used as the refractive index of the sample.

[0589] [Table 2] Polymerizable monomers Refractive index Example 1 M-1 1.658 Example 2 M-2 1.666 Example 3 M-3 1.664 Example 4 M-4 1.696 Example 5 M-5 1.680 Example 6 M-6 1.654 Example 7 M-7 1.664 Example 8 M-8 1.664 Example 9 M-9 1.688 Example 10 M-10 1.672 Example 11 M-11 1.664 Example 12 M-12 1.667 Example 13 M-13 1.701 Example 14 M-14 1.670 Example 15 M-15 1.654 Example 16 M-16 1.686 Example 17 M-17 1.707 Example 18 M-18 1.683 Example 19 M-19 1.741 Example 20 M-20 1.670 Example 21 M-21 1.680 Example 22 M-22 1.713 Example 23 M-23 1.675 Comparative Example 1 M-24 1.679 Comparative Example 2 M-25 1.692 Comparative Example 3 M-26 1.672 Comparative Example 4 M-27 1.691

[0590] As shown in Table 2, the refractive indices of the compounds in the examples are all 1.65 or higher, and these compounds all have sufficient refractive index as high refractive index monomers. As shown in Table 1, the holographic media containing the compounds of the examples have the same or higher total Δn compared to the holographic media containing the compounds of the comparative examples. Therefore, the compounds of the examples maintain the holographic recording performance while improving the compatibility with the medium, and are superior to the compounds of the comparative examples.

[0591] The present invention has been described in detail using specific examples, but it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention. This application is based on Japanese Patent Application 2021-49181, filed on March 23, 2021, and is incorporated herein by reference in its entirety. [Simplified Explanation of the Diagram]

[0023] Figure 1 is a schematic diagram showing the general structure of the apparatus used for holographic recording.

Claims

1. A compound represented by the following formula (1), [Chemical 1] [wherein, A represents (meth)acrylyl; L represents a branchable (n+1) valence linker; R1 represents an aromatic cyclic group that may have substituents; R2 represents a monovalent organic group that may have substituents; X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents, respectively; m represents an integer of 0 or 1; n represents an integer from 1 to 3; p represents an integer of 0 or 1; wherein, In the formula, the (meth)acrylic acid moiety is 1; in the formula, the two R1s can bond to each other at any position to form a ring structure; in the formula, R1 = R2, X1 = X2, and p = 1 do not all hold simultaneously.

2. The compound of claim 1, wherein R1 is a condensed aromatic ring group that may have substituents, or a monocyclic aromatic group substituted with an aromatic ring group.

3. The compound of claim 1 or 2, wherein the R2 has a partial structure represented by the following formula (2), [Chemical 2] [where J represents a carbon atom that may have a substituent or a nitrogen atom that may have a substituent, and G represents a sulfur atom, an oxygen atom or a nitrogen atom that may have a substituent].

4. A compound represented by the following formula (3), [Chemical 3] [wherein, R1 represents an aromatic cyclic group that may have substituents; R2 represents a monovalent organic group that may have substituents; wherein, R1 represents a sulfur-containing aromatic heterocyclic group that may have substituents, or an aromatic cyclic group that has a sulfur-containing aromatic heterocyclic group as a substituent, and / or, R2 has a benzothiazole ring; X1 and X2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents, respectively; p represents an integer of 0 or 1; where, the two R1s can bond to each other at any position to form a ring structure; where, in the formula, R1 = R2, X1 = X2, and p = 1 do not all hold simultaneously.

5. A method for manufacturing a compound as claimed in claim 4, characterized in that an aliphatic cyclic compound represented by the following formula (4) undergoes a ring-opening reaction, [Formula 4] [wherein, R1 represents an aromatic cyclic group that may have substituents; X1 represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents; p represents an integer of 0 or 1; Z represents an aliphatic linking group that may have substituents and be branched; r represents an integer of 0 or 1; wherein, two R1s may bond to each other at any position to form a ring structure].

6. A method for manufacturing the compound of claim 5, wherein the aliphatic cyclic compound represented by formula (4) above is a compound represented by formula (5) or formula (6) below, [Chemical 5] [wherein, R1 represents an aromatic cyclic group that may have substituents; X1 represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have substituents; p represents an integer of 0 or 1; where the two R1s may bond to each other at any position to form a ring structure].

7. A polymerizable composition comprising a compound as claimed in any one of claims 1 to 3 and a polymerization initiator.

8. A holographic recording medium comprising the polymeric composition as claimed in claim 7.

9. A polymer formed by polymerizing the polymeric composition of claim 7.

10. An optical material comprising the polymer as claimed in claim 9.

11. An optical component comprising the polymer as claimed in claim 9.

12. A high-capacity memory comprising a holographic recording medium as claimed in claim 8.

13. An optical element obtained by holographic recording on a holographic recording medium as claimed in claim 8.

14. An AR glasses comprising the optical elements of claim 13.

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