Compounds, methods of making the same, polymerizable compositions, polymers, holographic recording media, optical materials, and optical components

Abstract

The present application is a compound represented by the following formula (1). The present application provides a compound having high refractive index and excellent polymerizability, which is useful as a raw material for optical materials and the like. [In the formula, A represents a polymerizable group. L represents a branched or unbranched (n+1)-valent linking group. R 1 represents an aromatic ring group with or without a substituent. R 2 represents a monovalent organic group with or without a substituent. X 1 , X 2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without a substituent. 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, 2 R 1 may be bonded to each other at any position to form a ring structure. Among them, in the formula, R 1 = R 2 , X 1 = X 2 , and p = 1 do not all hold simultaneously].

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 materials, and optical components using a polymerizable composition comprising this compound or a polymer thereof. Background Technology

[0002] Traditionally, glass has been the most commonly used optical material. For example, in the case of optical lenses, even lenses with the same focal length can be made thinner by using a high-refractive-index material, resulting in advantages such as lightweight construction and increased design freedom for optical paths. Furthermore, high-refractive-index optical lenses are also effective for miniaturizing, increasing resolution, and widening the angle of view in optical imaging devices.

[0003] In recent years, highly transparent plastics have attracted attention as an optical material alternative to glass. Compared to glass, plastic materials have advantages such as ease of weight reduction, ease of improving mechanical strength, and ease of processing and shaping. With the development of related technologies, the performance requirements for plastic optical materials are constantly increasing. For example, materials used in optical lenses are required to be easy to polymerize (polymerizability), have good curing properties, and have a high refractive index.

[0004] To date, a variety of resins have been developed to improve the refractive index. For example, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is 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 hardly considered high enough (Patent Document 1). To increase the refractive index, introducing sulfur atoms into the molecule, in addition to introducing aromatic rings, is effective. For example, Patent Document 2 describes a diacrylate monomer having a pentaerythritol skeleton with 1 to 2 naphthalene thio 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 two benzothiazole rings within one molecule. In this case, the refractive index is 1.63. These are insufficient for applications requiring ultra-high refractive indices exceeding 1.65.

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

[0006] Patent Document 6 relates to an optical material used in a holographic recording medium. As an ultra-high refractive index compound, Patent Document 6 describes a pentaerythritol-type (meth)acrylate compound having three aromatic rings. These compounds achieve high refractive indices through a structure having three identical high-refractive sites. However, sometimes sufficient polymerization properties cannot be obtained due to steric hindrance around the polymerizable groups, leading to a reduction in holographic recording properties.

[0007] [Patent Document 1] Japanese Patent Application Publication No. 6-220131 [Patent Document 2] Japanese Patent 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 objective of this invention is to provide a compound that combines high refractive index, high transparency, and easy polymerization properties, which can be used as an optical material or optical component.

[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 exhibit high refractive index and high transparency.

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

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

[0012] [Chemistry 1]

[0013] [In the formula, A represents a polymerizable group. L represents a branched or unbranched (n+1) valence linkage group. R] 1 Indicates an aromatic cyclic group with or without substituents. R 2 X represents a monovalent organogroup, with or without substituents. 1 X 2 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. 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, there are 2 Rs 1 They can bond to each other at any position to form a ring structure. Where, R 1 =R 2 X 1 =X 2 (not all of the above are true simultaneously.) [2] The compound described in [1], wherein the number of polymeric groups in the above formula (1) is 1. [3] The compound described in [1] or [2], wherein A is ethylene oxide, vinyl, allyl, or (meth)acryloyl. [4] The compound as described in [3], wherein A is (meth)acryloyl. [5] The compound as described in any one of [1] to [4], wherein the above R 1 It is a fused aromatic ring group with or without substituents, or a monocyclic aromatic group substituted with an aromatic ring group. [6] The compound as described in any one of [1] to [5], wherein the above R 2 It has the partial structure shown in the following formula (2).

[0014] [Chemistry 2]

[0015] [In the formula, J represents a carbon atom with or without a substituent, or a nitrogen atom with or without a substituent; G represents a sulfur atom, an oxygen atom, or a nitrogen atom with or without a substituent]. [7] A compound represented by the following formula (3),

[0016] [Chemistry 3]

[0017] [In the formula, R] 1 Indicates an aromatic cyclic group with or without substituents. R 2 X represents a monovalent organogroup, with or without substituents. 1 X 2 Each of the following can be used to represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. p represents an integer, either 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure. Where, R 1 =R 2 X 1 =X 2 (not all of the above are true simultaneously.) [8] A method for manufacturing a compound as described in [7], characterized in that an aliphatic cyclic compound represented by the following formula (4) is subjected to a ring-opening reaction.

[0018] [Chemistry 4]

[0019] [In the formula, R] 1 Indicates an aromatic cyclic group with or without substituents. X 1 Represents an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. p represents an integer of 0 or 1. Z represents an aliphatic linker with or without substituents and branched or unbranched. r represents an integer of 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure. [9] The method for manufacturing the compound as described in [8], wherein the aliphatic cyclic compound represented by formula (4) above is a compound represented by formula (5) or formula (6) below.

[0020] [Chemistry 5]

[0021] [In the formula, R] 1 Indicates an aromatic cyclic group with or without substituents. X 1 This represents an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. p represents an integer, either 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure.

[10] A polymerizable composition comprising any one of [1] to [6] a compound and a polymerization initiator.

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

[10] .

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

[10] .

[13] An optical material comprising the polymer described in

[12] .

[14] An optical component comprising the polymer described in

[12] .

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

[11] .

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

[11] .

[17] An AR glasses comprising the optical element described in

[16] . [Invention Effects]

[0022] According to the present invention, a high refractive index compound that combines high transparency and easy polymerization can be provided and can be used as an optical material. The compounds of the present invention are particularly useful as reactive compounds used in hard coatings of optical lenses or optical components, and in holographic recording media. By using the compounds of the present invention, it is possible to achieve optical materials and optical components with high diffraction efficiency, high light transmittance, and low turbidity. Attached Figure Description

[0023] Figure 1 A schematic diagram illustrating the general structure of the apparatus used for holographic recording. [Symbol Explanation] 1: LED unit L1: Recording light semiconductor laser source L2: Laser source for reproducing light M1, M2, M3: Mirror PBS: Polarizing Spectroscope PD1, PD2, PD3: Photodetectors S: Holographic recording medium Detailed Implementation

[0024] The embodiments of the present invention will now be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within its scope. In this invention, "(meth)acrylate" is a general term for acrylates and methacrylates. "(meth)acryloyl" is a general term for acryloyl groups and methacryloyl groups. In this invention, "having or not having substituents" means having or not having one or more substituents. "Nitrogen atoms having or not having substituents" also includes imine groups, etc., when they do not have substituents.

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

[0026] [Chemistry 6]

[0027] [In the formula, A represents a polymerizable group. L represents a branched or unbranched (n+1) valence linkage group. R] 1 Indicates an aromatic cyclic group with or without substituents. R 2 X represents a monovalent organogroup, with or without substituents. 1 X 2 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. 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, there are 2 Rs 1 They can bond to each other at any position to form a ring structure. Where, R 1 =R 2 X 1 =X 2 (not all of the above are true simultaneously.)

[0028] 1-1. Regarding the structure of the compound of formula (1), The compound of formula (1) has a pentaerythritol backbone, and one of the four molecular chains bonded to its quaternary carbon atom has a polymerizable group. Furthermore, at least one of the remaining three molecular chains exhibits a structure with a high refractive index. This further enhances the refractive index of the polymer. Moreover, in the compound shown in formula (1), two of these remaining three molecular chains have the same structure, and one has a different structure. This further enhances the transparency of the polymer. A different structure refers to -X in formula (1). 2 -R 2 The molecular chain shown has a structure similar to -(X) 1 ) p -R 1 The molecular chains shown are different. Even if they respectively constitute R 1 With R 2 X 1 With X 2 If elements, partial structures, and quantities are the same, but their bonding positions differ, they are considered as -X. 2 -R 2 Compared to -(X) 1 ) p -R 1 In other words, it is a heterogeneous structure.

[0029] 1-2. Regarding A in equation (1) A represents a polymerizable group, the structure of which is not particularly limited. Examples of polymerizable groups include: (meth)acryloyl, allyl, vinyl, vinyl-substituted phenyl, isopropenyl-substituted phenyl, vinyl-substituted naphthyl, isopropenyl-substituted naphthyl, ethylene oxide, 2-methylethylene oxide, oxetyl, 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)acryloyl are preferred. Among these, (meth)acryloyl is more preferred due to its higher reactivity.

[0030] 1-3. Regarding L in equation (1) L represents a branched or unbranched (n+1) valence linker. L does not necessarily have to contain a heteroatom, but from the viewpoint of ease of synthesis, it is preferred to have an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents.

[0031] From the viewpoint of imparting high solubility of the compound of formula (1) in various media and avoiding staining, L is preferably an aliphatic hydrocarbon group having oxygen atoms, sulfur atoms, or nitrogen atoms with or without substituents. The number of carbon atoms in this aliphatic hydrocarbon group (excluding the number of carbon atoms of substituents) is preferably 1 to 8. If the number of carbon atoms in this 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 a combination of these structures. From the viewpoint of reducing steric hindrance around the polymerizable group A, a chain aliphatic hydrocarbon group is preferred.

[0032] Examples of chain-like aliphatic hydrocarbon groups constituting L, having oxygen or sulfur atoms, or nitrogen atoms with or without substituents, when n=1, include: oxoylidene methylene, oxoylidene ethoxy, 1,3-oxoylidene propionyl, 1,2-oxoylidene propionyl, oxoylidene butylidene, 2-hydroxyoxoylidene propionyl, oxoylidene hexyl, oxoylidene heptyl, 3-oxoylidene pentyl, -OCH2CH2NHC(O)-, -OCH2CH2OCH2CH2NHC(O)-, -OCH2CH2SCH2CH2-, -OCH2CH2NHC(S)-, -OCH2CH2OCH2CH2NHC(S)-, -OCH2CH2SCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, etc. L can also be composed of two or more of these groups. Examples of L as n=2 or 3 include -(OCH2)2C(CH3)NHC(O)-, and linking groups formed by replacing any hydrogen atom in the aforementioned chain-like aliphatic hydrocarbon group with a bonding site to the polymerizable group A. In this case, it can also bond to the polymerizable group through a branched structure.

[0033] From the perspective of high refractive index, L is preferably a cyclic group, and the rings contained in the cyclic group constituting L can be monocyclic or fused 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 while maintaining a high refractive index, aromatic hydrocarbon rings are preferred. Examples of aromatic hydrocarbon rings constituting L include: benzene rings, indene rings, naphthalene rings, azulene rings, fluorene rings, acenaphthene rings, anthracene rings, phenanthrene rings, pyrene rings, etc.

[0034] L may or may not have substituents. Examples of substituents that L may have include: halogen atoms (chlorine, bromine, iodine), hydroxyl, mercapto, alkyl with 1 to 8 carbon atoms, alkenyl with 2 to 8 carbon atoms, alkoxy with 1 to 8 carbon atoms, phenyl, 2,4,6-trimethylyl (mesityl group), tolyl, naphthyl, cyano, acetoxy, alkyl carbonyloxy with 2 to 9 carbon atoms, alkoxy carbonyl with 2 to 9 carbon atoms, aminosulfonyl, alkyl aminosulfonyl with 2 to 9 carbon atoms, alkyl carbonyl with 2 to 9 carbon atoms, phenethyl, hydroxyethyl, acetamyl, dialkylaminoethyl bonded with alkyl with 1 to 4 carbon atoms, trifluoromethyl, alkylthio with 1 to 8 carbon atoms, aromatic ring thio with 6 to 10 carbon atoms, nitro, etc.

[0035] 1-4. Regarding X in equation (1) 1 X 2 X 1 X 2 Each can be represented independently as an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. Based on the consideration of minimizing water absorption, X... 1 X 2 The nitrogen atom is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom that provides a high refractive index. There are no particular limitations on the groups that can be substituted on the nitrogen atom, but aromatic hydrocarbon groups such as alkyl, phenyl, or naphthyl with 1 to 8 carbon atoms, such as methyl or ethyl, are preferred.

[0036] 1-5. Regarding R in equation (1) 1 R 1 This indicates an aromatic ring group with or without substituents. It constitutes R. 1 Aromatic rings are broadly classified 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, etc. Rings, including diphenylene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings. 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, oxazole rings, thiazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, thiadiazole rings, etc., containing two or more heteroatoms; benzoxazole rings, thiophene-oxazole rings, thiazoxazole-oxazole rings, oxazoloxazole-oxazole rings, oxazoloxazole-oxazole rings, oxazoloxazole-oxazole rings, etc. Imidazole ring, oxazolopyridine ring, oxazolopyridazine ring, oxazolopyrimidine ring, oxazolopyridazine ring, naphthooxazole ring, quinolineoxazole ring, dioxazolopyridazine ring, phenoxazine ring, benzothiazazole ring, N-[4-(5-nitro-2-furanyl)-2-thiazolyl]acetamide (furathiazole) ring, thienothiazazole ring, thiazonothiazazole ring, thiazonoimidazazole ring, thienothiadiazole ring, thiazonothiadiazole ring, thiazopyridine ring, thiazopyridazine ring, thiazonopyrimidine ring, thiazonopyridazine ring, naphthothiazazole ring, quinolinethiazazole ring, dithioxanthracene ring, and phenthiazine ring, etc., including aromatic heterocycles containing two or more heteroatoms, are rings formed by the condensation of two or three rings.

[0037] As a component of R 1 The aromatic hydrocarbon rings are preferably benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, pyrene rings, biphenylide rings, or fluorene rings, based on their ease of synthesis and availability. Based on the viewpoint of suppressing the fluorescence of compounds of formula (1), R... 1 The aromatic hydrocarbon ring is more preferably a benzene ring, a naphthalene ring, a biphenylene ring, or a fluorene ring.

[0038] As a component of R 1 The aromatic heterocycle, based on the tendency to increase the refractive index of the compound of formula (1), is preferably a sulfur-containing aromatic heterocycle. 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 oxygen and nitrogen atoms. Considering the avoidance of coloring 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; dithioxanthracene rings and other aromatic heterocycles containing two or more sulfur atoms; thiazole rings, isothiazole rings, benzothiazole rings, naphthothiazole rings, phenothiazine rings, thiazole-imidazolium rings, thiazole-pyridine rings, thiazole-pyridazine rings, thiazole-pyrimidine rings, dioxazolopyrazine rings, thiazole-pyrazine rings, thiazole-oxazole rings, dibenzobenzothiophene rings, thiazole-oxazole rings, thiazole-thiadiazole rings, thiazole-thiadiazole rings, etc., are aromatic heterocycles containing two or more types of heteroatoms. The sulfur-containing aromatic heterocyclic ring can be a monocyclic or a fused ring. From the viewpoint of increasing the refractive index, a fused ring is preferred. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and more preferably 2 to 5, considering the ease of obtaining raw materials or the ease of synthesis. In particular, considering the improvement of refractive index and low colorability, sulfur-containing aromatic heterocycles are preferably benzothiazole rings, dibenzothiophene rings, benzothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, and dithionanthracene rings.

[0039] As a component of R 1 The aromatic heterocycle, based on its ease of synthesis, can also be a nitrogen-containing aromatic heterocycle. 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. To avoid 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, oxazole rings, thiazole rings, benzo[a]oxazole rings, naphtho[a]oxazole rings, benzo[a]thiazine rings, phenothiazine rings, thieno[a]oxazole rings, thiazo[a]oxazole rings, N-[4-(5-nitro-2-furanyl)-2-thiazolyl]acetamide rings, thieno[a]thiazine rings, and thiazo[a]thiazine rings, etc., containing one nitrogen atom. Aromatic heterocycles; including imidazole rings, triazole rings, tetraazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, thiadiazole rings, benzimidazole rings, oxazoloimidazolium rings, oxazolopyridine rings, oxazolopyridazine rings, oxazolopyridine rings, quinoline oxazole rings, dioxazolopyridine rings, thiazolidinazole rings, thienothiadiazole rings, thiazolidinazole rings, thiazolidinazole rings, thiazolidinazole rings, thiazolidinazole rings, thiazolidinazole rings, quinoline thiazolidinazole rings, etc., aromatic heterocycles containing two or more nitrogen atoms.

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

[0041] As a component of R 1 The aromatic heterocycle can also be an oxygen-containing aromatic heterocycle. Therefore, there is a tendency 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 may 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, phenoxazine ring, oxazole ring, isoxazole ring, benzooxazole ring, benzoisooxazole ring, naphthooxazole ring, thienooxazole ring, thiazonooxazole ring, oxazoloimidazolium ring, N-[4-(5-nitro-2-furanyl)-2-thiazolyl]acetamide ring, etc.; and aromatic heterocycles containing two or more oxygen atoms, such as dibenzodioxane-hexene ring, oxazolonooxazole ring, and dioxazolopyrazine ring.

[0042] The oxygen-containing aromatic heterocycle can be a monocyclic or a fused ring. From the viewpoint of increasing the refractive index, a fused ring is preferred. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and more preferably 2 to 5, considering the ease of obtaining raw materials or the ease of synthesis. In particular, considering the improvement of 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 isoxazole ring, a benzoxazole ring, a benzoisoxazole ring, or a naphthoxazole ring, and more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, or a benzoxazole ring.

[0043] These constitute R 1The aromatic ring may or may not have substituents. Possible substituents include, for example, halogen atoms such as chlorine, bromine, and iodine; alkyl groups with 1 to 8 carbon atoms, alkenyl groups with 2 to 8 carbon atoms, alkoxy groups, cyano groups, acetoxy groups, alkyl carbonyloxy groups with 2 to 9 carbon atoms, alkoxy carbonyl groups with 2 to 9 carbon atoms, aminosulfonyl groups, alkyl aminosulfonyl groups with 2 to 9 carbon atoms, alkyl carbonyl groups with 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetamyl groups, dialkylaminoethyl groups formed by alkyl bonds with 1 to 4 carbon atoms, trifluoromethyl groups, alkylthio groups with 1 to 8 carbon atoms, aromatic ring thio groups with 6 to 10 carbon atoms, and nitro groups. Among them, the preferred examples are: alkyl with 1 to 8 carbon atoms, alkoxy with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms, aromatic cyclothio with 6 to 10 carbon atoms, cyano, acetoxy, alkyl carboxyl with 2 to 8 carbon atoms, aminosulfonyl, alkyl aminosulfonyl with 2 to 9 carbon atoms, and nitro.

[0044] Regarding these components R 1 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 and the constituent R 1 The aromatic ring is synonymous with the aromatic ring that constitutes R. The aromatic ring contained in these substituents can be related to the aromatic ring that constitutes R. 1 The aromatic rings can be directly bonded at any position, or via oxygen atoms, sulfur atoms, or nitrogen atoms with or without substituents to form R. 1 The aromatic ring bonding can also be achieved via any linker group and the constituent R. 1 Aromatic ring bonding. Substituents are more preferably directly bonded.

[0045] Furthermore, by setting the aromatic ring contained in the substituent to 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 related to R... 1 The sulfur-containing aromatic heterocycle is synonymous with the sulfur-containing aromatic heterocycle. More preferably, it is a fused ring, and even more preferably, it is a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, or a dithionanthracene ring.

[0046] R 1 There is no particular limitation on the number of aromatic rings of the substituents, but from the viewpoint of ease of synthesis and solubility, 1 to 4 is preferred, and 1 to 2 is even more preferred.

[0047] Regarding the composition of R 1 The aromatic ring, based on the viewpoint of balancing high refractive index and high solubility in various media, is preferably a fused aromatic ring with or without substituents, or a monocyclic aromatic ring substituted with an aromatic ring group, more preferably a fused aromatic heterocycle with or without substituents, or an aromatic hydrocarbon ring having an aromatic heterocycle as a substituent.

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

[0049] Composition of R 1 The aromatic ring, when p=1, can interact with X in equation (1). 1 Bonded at any position. When p=0, R is formed. 1 The aromatic ring 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 while achieving a higher refractive index, the two Rs in equation (1) 1 Preferably, the structures are bonded together at any position to form a ring structure. On the other hand, in order to maintain the overall flexibility of the molecule while achieving higher solubility in various media, the two Rs in equation (1) 1 Preferably, they are not mutually bonded.

[0051] 1-6. Regarding R in equation (1) 2 R 2 R represents a monovalent organogroup. 2 It can be any of the following: linear, branched, or cyclic. In addition, these structures can be combined according to the physical properties required by the compound of formula (1). As long as -X in equation (1) 2 -R 2 For the above heterogeneous structures, then R 2 It can be selected from the above R 1 The structure in R can also be related to R. 1 Same structure.

[0052] From the perspective of increasing the refractive index of the compound of formula (1), R 2 Preferably, it has a ring structure. This ring structure can be a monocyclic structure or a fused ring structure. Based on the high solubility of the compound of formula (1) in various media, R is constructed... 2 The number of rings is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. Composition of R 2The ring does not necessarily need to be aromatic, but considering the trend of keeping the size small in the overall molecule while achieving a high refractive index, it is preferred to have an aromatic hydrocarbon ring or an aromatic heterocycle as the ring structure.

[0053] As a component of R 2 Aromatic hydrocarbon rings can be exemplified by: benzene ring, indene ring, naphthalene ring, azurite ring, fluorene ring, acenaphthene ring, anthracene ring, phenanthrene ring, pyrene ring, etc. As a component of R 2 Aromatic heterocycles can be exemplified as follows: furan ring, benzofuran ring, dibenzofuran ring, naphthofuran ring, benzonaphthofuran ring, dinaphthofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, naphthothiophene ring, benzonaphthothiophene ring, dinaphthothiophene ring, pyrrole ring, indole ring, carbazole ring, pyridine ring, quinoline ring, isoquinoline ring, etc., aromatic heterocycles containing one heteroatom; imidazole ring, triazole ring, tetraazole ring, oxazole ring, thiazole ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, thiadiazole ring, etc., aromatic heterocycles containing two or more heteroatoms; benzoxazole ring, thiophene-oxazole ring, thiazoxazole-oxazole ring, oxazolo ... Imidazole ring, oxazolopyridine ring, oxazolopyridazine ring, oxazolopyrimidine ring, oxazolopyrazine ring, naphthooxazole ring, hydroxyquinoline oxazole ring, dioxazolopyrazine ring, phenoxazine ring, benzothiazazole ring, N-[4-(5-nitro-2-furanyl)-2-thiazolyl]acetamide ring, thienothiazazole ring, thiazonothiazazole ring, thiazonoimidazazole ring, thienothiadiazole ring, thiazonopyridine ring, thiazonopyridazine ring, thiazonopyrimidine ring, thiazonopyrazine ring, naphthothiazazole ring, quinolinethiazazole ring, dithioxanthracene ring, and phenthiazine ring, etc., including aromatic heterocycles containing two or more heteroatoms, are rings formed by the condensation of two or three rings.

[0054] Considering the ease of synthesis of the compound based on formula (1), R 2 Preferably, it has a heterocyclic structure, and more preferably, it has a structure that includes an azole ring as a nitrogen-containing five-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, 1,2,5-oxadiazole rings, thiadiazole rings, tetraazole rings, etc. Based on the aspect of obtaining the target analyte efficiently, R... 2 A further preferred embodiment is a partial structure as shown in formula (2) below.

[0056] [Chemistry 7]

[0057] [In the formula, J represents a carbon atom with or without a substituent or a nitrogen atom with or without a substituent, and G represents a sulfur atom, an oxygen atom, or a nitrogen atom with or without a substituent.]

[0058] The partial structure shown in Formula (2) can be selected appropriately as needed. Based on the ease of synthesis of the compound of Formula (1) or its high solubility in various media, it is more preferably a thiazole ring, an oxazole ring, an imidazole ring, or a thiadiazole ring.

[0059] As mentioned above, considering the increased refractive index of the compound of formula (1), R 2 Preferably, it has an aromatic heterocycle, but more preferably a fused aromatic heterocycle. As R 2 Examples of fused aromatic heterocycles include indole rings, benzothiazole rings, benzoxazole rings, and benzimidazole rings. Considering the tendency to achieve both the high refractive index and high solubility of compounds of formula (1), benzothiazole rings are preferred.

[0060] The above R 2 The ring structure can be positioned arbitrarily with X 2 Direct bonding, or via an aliphatic linker with or without substituents and X. 2 Bonding. Considering the improved solubility of the compound of formula (1) in various media, the aliphatic linker is preferably chain-like. By partially converting the chain-like portion into an aliphatic hydrocarbon group, its solubility tends to be further improved. In this case, the number of carbon atoms (excluding the number of carbon atoms of the substituents) is preferably 1 to 8. By making the number of carbon atoms 8 or less, the refractive index is 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, ethoxy, propylene, 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, R 2 The ring structure may or may not have substituents. As R 2 Possible substituents include, for example: halogen atoms such as chlorine, bromine, and iodine; alkyl groups with 1 to 8 carbon atoms, alkenyl groups with 2 to 8 carbon atoms, aromatic hydrocarbon rings with 1 to 14 carbon atoms, aromatic heterocycles, alkoxy groups, cyano groups, acetoxy groups, alkyl carbonyloxy groups with 2 to 9 carbon atoms, alkoxy carbonyl groups with 2 to 9 carbon atoms, aminosulfonyl groups, alkyl aminosulfonyl groups with 2 to 9 carbon atoms, alkyl carbonyl groups with 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetamino groups, dialkylaminoethyl groups formed by alkyl groups with 1 to 4 carbon atoms, trifluoromethyl groups, alkylthio groups with 1 to 8 carbon atoms, aromatic ring thio groups with 6 to 10 carbon atoms, and nitro groups. Among them, based on the consideration of ease of acquisition, the following are preferably examples: alkyl with 1 to 8 carbon atoms, aromatic hydrocarbon ring with 1 to 14 carbon atoms, aromatic heterocycle, alkoxy with 1 to 8 carbon atoms, cyano, acetoxy, alkyl carboxyl with 2 to 8 carbon atoms, aminosulfonyl, alkyl aminosulfonyl with 2 to 9 carbon atoms, and nitro. Additionally, in R 2 In the case of a ring structure, from the viewpoint of increasing the refractive index of the compound of formula (1), it is also appropriate to choose a group that further contains an aromatic ring as a substituent. The aromatic ring contained in the substituent and the constituent R 1 The aromatic ring is synonymous with R. The aromatic ring contained in these substituents can be related to R. 2 The ring structure can be directly bonded at any position, or via oxygen atoms, sulfur atoms, or nitrogen atoms with or without substituents to R. 2 The ring structure bonding can also be achieved via any linker base with R. 2 The ring structure is bonded. The substituent is more preferably associated with R. 2 The ring structure is directly bonded.

[0062] 1-7. Regarding m and n in equation (1) m represents an integer of 0 or 1. This m can be appropriately chosen, and from the viewpoint of reducing the steric hindrance around the polymerizable group A and improving the reactivity of the compound of formula (1), m = 1 is preferred.

[0063] n represents an integer from 1 to 3. This n can also be chosen appropriately. For example, based on the viewpoint of making the compound of formula (1) readily polymerizable, n can be set to 2 or 3. On the other hand, considering the potential to increase the refractive index, the compound of formula (1) is preferably a monofunctional compound with fewer polymerizable groups, and more preferably a compound with only one polymerizable group. That is, from the viewpoint of increasing the refractive index, n = 1 or 2 is preferred, and more preferably n = 1.

[0064] 1-8. Molecular weight From the viewpoint of suppressing viscosity to maintain good processability, the compound of formula (1) is preferably with a molecular weight of 2000 or less, more preferably 1500 or less. From the viewpoint of reducing shrinkage during polymerization, the compound of formula (1) is preferably with a molecular weight of 400 or more, more preferably 500 or more, and even more preferably 550 or more.

[0065] 1-9. The Relationship Between Molecular Structure and Physical Properties The compound of formula (1) has the following characteristics: one of the four molecular chains of the pentaerythritol backbone has a polymerizable group, and at least one of the remaining three molecular chains exhibits a high refractive index structure, thus it can be used as a polymerizable compound (monomer) with a high refractive index. In particular, by appropriately introducing high refractive index sites with heterogeneous structures 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 media after polymerization. For example, using molecular chain -(X 1 ) p -R 1 Achieving high refractive index. Utilizing molecular chain -X 2 -R 2 This ensures high compatibility in the target medium. As a result, a high-refractive-index, high-transparency polymer with low turbidity can be obtained.

[0066] 1-10.Exemplary compounds The following are specific examples of compounds represented by formula (1) above. The compounds of the present invention are not limited to these examples without departing from the spirit of the invention.

[0067] [Chemistry 8]

[0068] [Chemistry 9]

[0069] [Chemistry 10]

[0070] [Chemistry 11]

[0071] [Chemistry 12]

[0072] [Chemistry 13]

[0073] 1-11. Regarding the synthesis method Compounds of formula (1) can be synthesized by combining various known methods. For example, they can be synthesized by reacting a compound of formula (3) with a compound having a group capable of reacting with a hydroxyl group.

[0074] [Chemistry 14]

[0075] [In the formula, R] 1 Indicates an aromatic cyclic group with or without substituents. R 2 X represents a monovalent organogroup, with or without substituents. 1 X 2 Each of the following can be used to represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. p represents an integer, either 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure. Where, R 1 =R 2 X 1 =X 2 (not all of the above are true simultaneously.)

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

[0077] [Chemistry 15]

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

[0079] The (meth)acrylate esterifying agent can be any compound that has a (meth)acryloyl group or a group that can be converted into a (meth)acryloyl group and can react with the active hydrogen of the hydroxyl group in formula (3). Examples of (meth)acrylate esterifying agents include: (meth)acryloyl chloride, (meth)acrylic anhydride, (meth)acrylate, 3-chloropropionyl chloride, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethoxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)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) is 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 a combination of one or more organic basic compounds and one or more inorganic basic compounds.

[0082] In the reaction of the compound of formula (3) with the (meth)acrylate esterifying agent, an organic solvent is preferably used. 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. Low staining can be achieved by removing impurities through purification. Known methods can be used as purification methods. For example, purification can be carried out 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, considering the ease of removing coloring substances.

[0085] Examples of suitable solvents for recrystallization 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-dioxane; 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; nitrile solvents 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. These solvents can be used individually or in combination of two or more.

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

[0087] For example, despite the low yield and high loading of the purified compound, 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 a nucleophilic substitution reaction to pentaerythritol trihalogenated compound (b).

[0088] [Chemistry 16]

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

[0090] [Chemistry 17]

[0091] [In the formula, R] 1 Indicates an aromatic cyclic group with or without substituents. X 1 Represents an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. p represents an integer of 0 or 1. Z represents an aliphatic linker with or without substituents and branched or unbranched. r represents an integer of 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure.

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

[0093] When r = 1, Z represents an aliphatic linker that has or does not have substituents and is either branched or unbranched. Examples of aliphatic cyclic compounds of formula (4) include: cyclic carbonate compounds, cyclic carbamate compounds, cyclic thiocarbonate compounds, cyclic thiocarbamate 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 appropriately selected as needed. Considering the availability of compounds that combine high refractive index and high solubility, the aliphatic cyclic compound of formula (4) is preferably an oxetane compound as shown in formula (5) below, or a cyclic carbonate compound as shown in formula (6) below.

[0095] [Chemistry 18]

[0096] [In the formula, R] 1 Indicates an aromatic cyclic group with or without substituents. X 1 This represents an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. p represents an integer, either 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure.

[0097] <Example of synthesis of aliphatic cyclic compounds of formula (4) with r=1> As shown in the following reaction formula, any one of the following reagents (d) – a cyclic carbonate esterifying agent, a cyclic carbamate esterifying agent, a cyclic thiocarbonate esterifying agent, a cyclic thiocarbamate esterifying agent, a cyclic sulfate esterifying agent, a cyclic sulfite esterifying agent, and a cyclic phosphorylation esterifying agent – ​​is applied to pentaerythritol trihalide (b) to obtain intermediate (e). Further linking the compound (c-1) with the high-refractive-index site to intermediate (e) yields the aliphatic cyclic compound of formula (4).

[0098] By having compound (f) act on intermediate (e) to pre-introduce a portion of the structure at the high refractive index, the obtained intermediate (g) is bonded to compound (h), thereby synthesizing aliphatic cyclic compounds of formula (4).

[0099] Instead of pentaerythritol trihalide (b), a compound (c-1) with a high refractive index is linked to pentaerythritol dihalide (i) to obtain intermediate (j). The reagent (d) is then applied to intermediate (j) to synthesize the aliphatic cyclic compound of formula (4).

[0100] By reacting a compound (c-2) with a high refractive index site with an aliphatic cyclic compound of formula (4), a high refractive index site can be introduced while opening the aliphatic cyclic structure, thereby synthesizing a compound of formula (3).

[0101] Compounds 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 compounds of formula (4) with r=0> In this case, the aliphatic cyclic compound of formula (4) is the oxobutane compound shown in (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 bonding a compound (c-1) with a high refractive index site.

[0104] By applying compound (f) to intermediate (k) and pre-introducing a portion of the structure at the high refractive index, the obtained intermediate (l) is bonded to compound (h), thereby synthesizing the compound of formula (5).

[0105] By reacting the compound (c-2) with the compound of formula (5), the high refractive index site can be introduced while the oxobutane structure is opened, thereby synthesizing the compound of formula (3).

[0106] [Chemistry 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. The polymer of the present invention can be obtained by polymerizing the polymerizable functional group A of the compound of formula (1) through a polymerization initiator.

[0108] 2-1. Polymerization initiator There are no particular limitations on the type of polymerization initiator; it is sufficient to select an appropriate initiator from the known sources, depending on the polymerization method. Furthermore, there are no limitations 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. In addition, the examples of polymerization initiators described below also include what are commonly referred to as polymerization catalysts.

[0110] 2-1-1. Free radical polymerization initiators <Photopolymerization Initiator> Regarding the photopolymerization initiator assisting the polymerization of the polymerizable composition of the present invention, any known photoradical polymerization initiator may be used. Examples include azo compounds, azido compounds, organic peroxides, organoborates, onium salts, diimidazole derivatives, titanoceramsite compounds, iodonium salts, organothiols, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfones, carbamic acid derivatives, sulfonamides, triarylethanols, and oxime esters. Among these, benzophenones, acylphosphine oxides, and oxime esters are preferred as photopolymerization initiators based on compatibility and ease of acquisition.

[0111] Specific examples of photopolymerization initiators include: benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, tert-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligomer {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzoyladium dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, methyl benzoate, ethyl benzoate, isopropyl benzoate, isobutyl benzoate, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholino)phenyl Phenyl)-Butanone-1, diethylthioxanone, isopropylthioxanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one and methyl benzoylcarbamate, 1-[4-(phenylthio)-2-(O-benzoyl oxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone, etc.

[0112] These photopolymerization initiators can be used individually or in combination or ratio of two or more.

[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 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 more preferably 3 parts by mass or less. If too much photopolymerization initiator is added, there is a concern that polymerization will proceed rapidly, resulting not only in increased birefringence of the cured body but also in a deterioration of color. On the other hand, if too little photopolymerization initiator is added, there is a concern that the polymerizable composition will not polymerize sufficiently.

[0114] <Thermal polymerization initiator> As a thermal polymerization initiator to assist 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: ketone 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 dicumene peroxide, etc. Dialkyl peroxides such as di-tert-butyl peroxide; dilauroyl peroxide, dibenzoyl peroxide, and other dialkyl peroxides; dicarbonates such as bis(4-tert-butylcyclohexyl) peroxide and bis(2-ethylhexyl) peroxide; and peroxide esters such as tert-butyl peroxide-2-ethylhexanoate, tert-hexyl peroxyisopropyl 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-dimethylpentanonitrile), 1,1'-azobis-1-cyclohexanenitrile, dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanopentanoic acid, and 2,2'-azobis-(2-amidinylpropane)dihydrochloride.

[0117] These thermal polymerization initiators can be used individually 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 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 more preferably 2 parts by mass or less. If there is too much thermal polymerization initiator, there is a concern that polymerization will proceed rapidly, which will not only impair the optical uniformity of the obtained polymer but also cause a deterioration in hue. On the other hand, if there is too little thermal polymerization initiator, there is a concern that thermal polymerization will not proceed sufficiently.

[0119] When photopolymerization initiators and thermal polymerization initiators are used together, their mass ratio is typically "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 may be insufficient polymerization; if there is too much thermal polymerization initiator, there is a concern about coloring.

[0120] 2-1-2. Redox polymerization initiators Redox polymerization initiators are free radical initiators that utilize redox reactions through a combination of peroxides and reducing agents. 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 persulfate, hydrogen peroxide, and hydroperoxide are combined with water-soluble inorganic reducing agents (Fe... 2+ It can be used in combination with organic reducing agents (such as NaHSO3, etc.) or organic reducing agents (such as alcohols and polyamines).

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

[0123] 2-1-3. Anionic polymerization initiators Examples of anionic polymerization initiators used in the polymerizable compositions of the present invention include: alkali metals, n-butyllithium, sodium amide, sodium naphthalenide, Grignard reagents, lithium alkoxides, alkali metal benzophenone ketyl, etc. 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 Examples of cationic polymerization initiators used in the polymerizable compositions of the present invention include: Brønsted 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 triphenylchloromethane. 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 or cationic polymerization initiator 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 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 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 is not induced; if more than 5 parts by mass are mixed, it is difficult to balance the applicable time and polymerization rate.

[0126] 2-1-5. Photocationic polymerization initiators The photocationic polymerization initiator in this invention is an initiator that generates cationic species through light. There are no particular limitations on the photocationic polymerization initiator; any compound that generates cationic species through light irradiation is acceptable. Onionium salts are commonly known. Examples of onionium salts include diazonium salts of Lewis acids, iodonium salts of Lewis acids, and sulfonium salts of Lewis acids. Specifically, examples include phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorus hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, and tri-4-methylphenylsulfonium salt of antimony tetrafluoride. Aromatic sulfonium salts are preferably used.

[0127] Specific examples of photocationic polymerization initiators include: S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)disulfonium bis(hexafluorophosphate), diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluoroantimonate, etc., for example, trade names such as: Dow Chemical's UVI-6992, SAN-APRO's CPI-100P, SAN-APRO's CPI-101A, SAN-APRO's CPI-200K, IGM Resins' Omnicat 270, etc.

[0128] These photocationic polymerization initiators can be used individually or in combination or ratio of two or more.

[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, 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 amount of photocationic polymerization initiator is less than 0.02 parts by mass, insufficient reaction will occur; if the amount of initiator exceeds 20 parts by mass, it will be difficult to balance the applicable time and polymerization rate.

[0130] In the use of photocationic polymerization initiators, the aforementioned cationic polymerization initiators may also be used concurrently. In this case, a 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, there is a concern that the polymerization rate will slow down; on the other hand, if the amount of cationic polymerization initiator used is too large, there is a concern that the physical properties of the obtained polymer will be reduced.

[0131] Furthermore, photocationic polymerization sensitizers can also be used concurrently with photocationic polymerization initiators. A photocationic polymerization sensitizer is a formulation that efficiently transfers the energy of the irradiation light to the photocationic polymerization initiator when the absorption wavelength of the light source used in photocationic polymerization does not match the wavelength of the initiator. Known examples include phenolic compounds such as methoxyphenol (Japanese Patent Application Publication No. 5-230189), thioxanthone 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 typically used in the range of 0.2 to 5 parts by weight, preferably 0.5 to 1 part by weight, relative to 1 part by weight of the photocationic polymerization initiator. If the amount of photocationic polymerization sensitizer is too small, the sensitizing effect may not be easily observed; on the other hand, if the amount of photocationic polymerization sensitizer is too large, there is a concern that the physical properties of the polymer may be reduced.

[0133] 2-2. On polymeric compounds The polymeric compounds contained in the polymeric composition of the present invention may individually include any one of the compounds of the present invention shown in formula (1), or may include two or more in any combination and ratio.

[0134] The polymeric compositions 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, preferably 5% by mass or more and 95% by mass or less, as a ratio relative to the total solid content of the polymeric composition of the present invention. 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 curability 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 cross-linked structures 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, their content, 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, particularly 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 for the properties imparted by the addition of other polymeric compounds to be insufficiently utilized. On the other hand, if the content of other polymeric compounds exceeds 5% by mass, there is a tendency for problems such as impaired optical properties or strength to easily occur.

[0138] <Catonic polymerizable monomers> Examples of cationic polymerizable monomers include: compounds with an ethylene oxide ring, styrene and its derivatives, vinyl naphthalene and its derivatives, vinyl ethers, N-vinyl compounds, and compounds with an oxobutane ring. Preferably, a compound having at least an oxetane ring is used, and more preferably, a compound having both an oxetane ring and an ethylene oxide ring is used.

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

[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-vinylphenothiazine, 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] These cationic polymerizable monomers can be used individually or in combination or ratio of two or more.

[0146] <Anionic polymerizable monomers> Examples of anionic polymerizable monomers include hydrocarbon monomers and polar monomers.

[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, nitroethylene, methylene malonate, cyanoacrylate, dicyanide, etc.).

[0149] These anionic polymerizable monomers can be used individually or in combination or ratio of two or more.

[0150] <Free radical polymerizable monomers> Compounds that have one or more vinyl unsaturated double bonds in one molecule of a free radical polymerizable monolayer include, for example, (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, secondary, or tert-)acrylate, amyl 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, benzyl chloromethacrylate, hydroxybenzyl methacrylate, ethyl hydroxyphenyl methacrylate, dihydroxyphenyl methacrylate, methyl furanate, tetrahydrofuranate, phenyl methacrylate, hydroxyphenyl methacrylate, propylene methacrylate, and more. Chlorophenyl ester, (meth)acrylate aminosulfonyl phenyl ester, (meth)acrylate-2-phenoxyethyl ester, (meth)acrylate-2-(hydroxyphenyl carbonyloxy)ethyl ester, phenol EO-modified (meth)acrylate, phenylphenol EO-modified (meth)acrylate, p-isopropylphenylphenol EO-modified (meth)acrylate, nonylphenol EO-modified (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, bisphenol F-EO-modified diacrylate, bisphenol A-EO Modified diacrylates, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentyl acrylate, tricyclodecane dimethylolpropane di(meth)acrylate, bisphenoxyethanol fluorene 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, N-(hydroxyphenyl)(meth)acrylamide, N-(aminosulfonylphenyl)(meth)acrylamide, N-(phenylsulfonyl)(meth)acrylamide, N-(tolylsulfonyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, etc.

[0153] Examples of vinyl esters include: vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoic acid vinyl, tert-butyl vinyl benzoate, vinyl chlorobenzoate, 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 derivatives include: styrene, p-acetylstyrene, p-benzoylstyrene, 2-butoxymethylstyrene, 4-butylstyrene, 4-sec-butylstyrene, 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] These free radical polymerizable monomers can be used individually or in combination or ratio of two or more.

[0156] The cationic polymerizable monomers, anionic polymerizable monomers, and free radical polymerizable monomers exemplified above can all be used. In addition, two or more types can be used in combination. When used as a holographic recording medium, as another polymeric compound used in conjunction with the compound of the present invention shown in formula (1), it is preferable to use a free radical polymeric monomer, because it is less likely to hinder the reaction that forms the resin matrix.

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

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

[0159] The polymerizable compositions of the present invention may also contain solvents to adjust viscosity.

[0160] Specific examples of solvents, depending on the properties of the polymerizable composition, include: 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 dioxane and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate; and acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones such as 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.; sulfoxides (amides such as dimethyl sulfoxide); nitriles such as acetonitrile and benzonitrile; organic solvents such as N-methylpyrrolidone.

[0161] These solvents can be used alone or in mixtures. Additionally, water may be used depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.). When using a solvent (or dispersion medium), there is no particular limitation on its amount, as long as it is adjusted and used in a way that results in a polymerizable composition of suitable viscosity, depending on the polymerization method, processing method, and application.

[0162] In this invention, in order to improve the heat resistance to yellowing or the weather resistance of the obtained polymer, it is preferable to mix 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], and other phenolic antioxidants; as well as triphenyl phosphite, triisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, tetra(C12~C14) phenolic antioxidants. Phosphorus-based antioxidants include (5-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] As an antioxidant, it is preferable to use a combination of phenolic antioxidants and phosphorus antioxidants. Examples of preferred combinations of phenolic and phosphorus antioxidants include: 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 mixed in the polymeric composition of the present invention, based on the consideration of making the obtained polymer have good heat resistance to yellowing, it 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.

[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 Inc.), and 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] With regard to improving the heat resistance to yellowing or weather resistance of the obtained polymer, 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 can be used alone or in combination of two or more.

[0169] 2-4 Method for manufacturing polymerizable compositions The polymerizable composition of the present invention can be manufactured by mixing the components, or by premixing 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 with active energy rays and methods of polymerization by heating.

[0171] 3-1. Polymerization Initiation Method (Active Energy Ray) In the case of photoradical polymerization of the polymerizable composition of the present invention, the polymerization is carried out by irradiation with active energy rays. The preferred active energy rays used are electron beams or light in the wavelength range from ultraviolet to infrared. As the light source, for example, if the active energy rays are 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; and 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 amount of irradiation by the active energy rays can be appropriately set according to the type of light source, the film thickness, etc. Preferably, the reaction rate of the total amount of polymerizable functional groups of the compound of the present invention shown in Formula (1) and other polymeric compounds is set to reach 80% or more, more preferably 90% or more. The reaction rate is calculated from the change in the intensity of the absorption peak of the polymerizable functional groups before and after the reaction based on the infrared absorption spectrum. After polymerization is carried out by irradiation with active energy rays, heat treatment or annealing can be performed as needed to further the polymerization. The preferred heating temperature is in the range of 80–200°C, and the preferred heating time is in the range of 10–60 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 both heating and cooling times are consumed, which is also often not economical.

[0174] 4. Polymers The polymers of the present invention, which are obtained by polymerizing the polymerizable compositions of the present invention, will be described below.

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

[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 detracts from the lightweight characteristics of plastics and is therefore not preferred. Furthermore, in the development of precision optical components such as lenses, it is important to achieve suitable optical properties for the component by combining optical materials with various refractive indices. Based on this viewpoint, polymers with a refractive index exceeding 1.63 are particularly useful as 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 is typically 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 for recording or reproduction.

[0178] 4-2. Glass transition temperature The glass transition 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, even more 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 the temperature is below this range, there is a concern that the optical properties may deviate from the design values ​​under the operating environment, and the required heat resistance may not be met. Furthermore, if the temperature is above this range, the processability of the polymer may decrease, making it impossible to obtain molded articles with good appearance or high dimensional accuracy. There is also a concern that 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 guide components, cover glass for display devices, light sensors, light switches, LEDs, light-emitting elements, light waveguides, light splitters, fiber optic 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. In addition, it can also be used as a layer for these. For example, display protective films can be cited.

[0181] In particular, considering the high refractive index properties 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-reflective properties, imparting high hardness, improving wear resistance, improving chemical resistance, imparting anti-fogging properties, or imparting a fashionable appearance.

[0182] 6. Holographic recording medium The polymerizable compositions of the present invention are suitable for use as recording layers in holographic recording media. Preferably, the polymerizable compositions of the present invention are photoreactive compositions that, in addition to the compounds of the present invention, also contain a matrix resin, a photopolymerization initiator and a free radical scavenger, and other additives. Details regarding their use as materials suitable for holographic recording media will be described below.

[0183] 6-1. Regarding the matrix resin, The polymerizable composition of the present invention preferably contains 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 is mainly a polymer containing 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 is formed between the materials, and light is refracted or reflected at the interface, causing light to leak into unwanted areas. Therefore, interference fringes may be distorted or cut and recorded in inappropriate areas, resulting in 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 compatibility of 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 variety of materials that are soluble in solvents in the polymeric composition, and may also be a resin formed by three-dimensional cross-linking of such resins after it has been formed to a working state. Examples of such resins include thermoplastic resins, thermosetting resins, and photocurable resins.

[0186] The three-dimensionally cross-linked resin is solvent-insoluble and is a cured product of a polymeric compound that is liquid at room temperature and a compound reactive to the polymeric compound. The three-dimensionally cross-linked resin acts as a physical barrier, thus suppressing volume changes during recording. That is, in the recorded 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 is more preferably 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. Thermoplastic resin 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 formal, polyvinylpyrrolidone, cellulose resins such as ethyl cellulose or nitrocellulose, polystyrene resin, and polycarbonate resin. These can be used individually or in combination of two or more.

[0188] As solvents for these thermoplastic resins, there are no particular restrictions on the solvents used, as long as they are capable of dissolving these resins. 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. Thermosetting resins When using thermosetting resins as the base resin, the curing temperature varies depending on the type of crosslinking agent or catalyst. Examples of combinations of functional groups that cure at room temperature include epoxy resin and amine, epoxy resin and thiol, and isocyanate and amine. Furthermore, examples of combinations using 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 insufficient time when forming materials such as holographic recording media. On the other hand, the latter allows for free selection of curing temperature or time by appropriately choosing the type and amount of catalyst, making it more suitable for curing materials such as holographic recording media. These 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 with two or more.

[0191] <Epoxides> Examples of epoxides include: polyglycidyl ether compounds of polyols such as polyethylene glycol, polypropylene glycol, tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxides with cyclic aliphatic groups having 4 to 7 membered rings, such as 3,4-epoxycyclohexylcarboxylate and 3,4-epoxy-1-methylhexanecarboxylate; bisphenol A type epoxides; hydrogenated bisphenol A type epoxides; bisphenol F type epoxides; and phenol or cresol phenolic varnish type epoxides.

[0192] The epoxide is preferably an epoxide having two or more epoxy groups per molecule, and there is no particular limitation on its type. If the number of epoxy groups is low, the hardness required as a matrix may not be achieved. There is no particular upper limit to the number of epoxy groups per molecule, but it is preferably usually 8 or less, especially 4 or less. If the number of epoxy groups is too high, it may take a long time to consume the epoxy groups, thus making the formation of the matrix resin too time-consuming.

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

[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, and 1,9-nonanedithiol; and polythiols such as THIOKOL (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 in the form of phenolic varnishes, and phenolic resins in the form of methyl phenolic resins.

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

[0197] <Amounts of amines, thiols, phenols, and acid anhydrides used> Regarding the amount of amines, thiols, phenols, and acid anhydrides used, the preferred ratio, based on the molar number of epoxy groups, is typically 0.1 equivalents or more, especially 0.7 equivalents or more, and typically 2.0 equivalents or less, especially 1.5 equivalents or less. If the amount of amines, thiols, phenols, or acid anhydrides used is too small or too large, there may be a large number of unreacted functional groups, which may compromise storage stability.

[0198] <Polymerization initiators for thermosetting resins> Anionic polymerization initiators and cationic polymerization initiators can be used as catalysts for curing thermosetting resins, depending on the curing temperature or curing time.

[0199] Anionic polymerization initiators generate anions through heat or active energy radiation; examples include amines. Examples of amines include amino-containing compounds such as dimethylbenzylamine, dimethylaminomethylphenol, and 1,8-diazabicyclo[5.4.0]undec-7-ene, and their derivatives; imidazole compounds such as imidazole, 2-methylimidazolium, and 2-ethyl-4-methylimidazolium, and their derivatives. One or more of these can be used depending on the curing temperature or curing time.

[0200] Cationic polymerization initiators generate cations through heat or active energy radiation; 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. Diaryliodoium salts and triarylsulfonium 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 relative to the matrix resin is preferably in the range of typically 0.001% by mass or more, especially 0.01% by mass or more and typically 50% by mass or less, especially 10% by mass or less. If the amount of polymerization initiator used in these thermosetting resins is too small, the concentration of the polymerization initiator is too low, and therefore the polymerization reaction sometimes takes too long. On the other hand, if the amount of polymerization initiator used in these thermosetting resins is too large, sometimes the continuous ring-opening reaction that is the polymerization reaction will no longer occur.

[0202] <Isocyanate> As an isocyanate, an isocyanate having two or more isocyanate groups per molecule is preferred, and there is no particular limitation on the type. If the number of isocyanate groups per molecule is low, the hardness required as a matrix resin may not be achieved. There is no particular upper limit to the number of isocyanate groups per molecule, but it is preferably usually 8 or less, especially 4 or less. If the number of isocyanate groups per molecule is too high, 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 upper limit to the number of isocyanate groups per molecule, but it is usually around 20 or less.

[0203] Examples of isocyanates include: aliphatic isocyanates such as hexamethylene diisocyanate, lysine methyl ester 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, and phenyl dimethyl diisocyanate; and polymers thereof, especially 3- to 7-mers.

[0204] In addition, examples include: the reaction products of water, trimethylolethane, trimethylolpropane and other polyols with the above 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 low, the crosslinking density increases, thus the hardness of the matrix resin becomes too high, which may lead to a decrease in recording speed. Furthermore, if the number average molecular weight is too high, 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] <Polyols> Examples of polyols include: polypropylene polyol, polycaprolactone polyol, polyester polyol, and polycarbonate polyol.

[0206] (Polypropylene polyol) Polypropylene polyols are obtained by reacting propylene oxide with a diol or polyol. Examples of diols 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, decanediol, polyethylene glycol, and polytetramethylene glycol. Commercially available polypropylene polyol products 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 polyols are 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, and β-methyl-ε-caprolactone.

[0208] Examples of diols 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, decanediol, polyethylene glycol, polytetramethylenediol, etc.

[0209] Commercially available products of polycaprolactone polyols obtained from the reaction of ε-caprolactone include: PLACEL 205, PLACEL 205H, PLACEL 205U, PLACEL 205UT, PLACEL 210, PLACEL 210N, PLACEL210CP, PLACEL 220, PLACEL 230, PLACEL 230N, PLACEL 240, PLACEL 220EB, PLACEL220EC, PLACEL 303, PLACEL 305, PLACEL 308, PLACEL 309, PLACEL 312, PLACEL320, PLACEL 401, PLACEL L205AL, PLACEL L212AL, PLACEL L220AL, PLACEL L320AL, PLACEL T2103, PLACEL T2205, PLACEL P3403, PLACEL 410 (both manufactured by Daicel Inc., trade names), etc.

[0210] (Polyester polyols) Examples of polyester polyols include polyester polyols obtained by polycondensation of dicarboxylic acid or its anhydride with a polyol.

[0211] Examples of dicarboxylic acids 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, decanediol, polyethylene glycol, polytetramethylenediol, etc.

[0213] Examples of polyester polyols include polyethylene glycol adipate, polybutylene glycol adipate, and polyhexamethylene glycol adipate. Commercially available products made from polyester polyols include: Adeka Newace F series, Adeka Newace Y series, Adeka Newace 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 de-alcoholization condensation reaction of diols with dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, etc.), those obtained by the dephenolization condensation reaction of diols with diphenyl carbonates, and those obtained by the de-diolization condensation reaction of diols with carbonates (e.g., ethylene carbonate, diethyl carbonate, etc.).

[0215] Examples of diols include aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and neopentanediol, as well as alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanediol.

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

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

[0218] (Molecular weight of polyols) The molecular weight of the polyols described above, 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. Furthermore, 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 Ingredients> In addition to the components mentioned above, the matrix resin in this embodiment may also contain other components, as long as they do not violate the spirit of this invention.

[0220] Other components include, for example, 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, decanediol, trimethylolpropane, polyethylene glycol, and polytetramethylene glycol, 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 urethane polymerization catalyst may also be included. Examples of onion salts used as catalysts for urethane polymerization include: bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonic acid, bis(4-tert-butylphenyl)iodonium p-toluenesulfonic acid, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonic acid, (4-bromophenyl)diphenylsulfonium trifluoromethanesulfonate, (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyliodonium perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium trifluoromethanesulfonic acid, and bis(alkylphenyl)iodonium hexafluorosulfonic acid; and Lewisite salts such as zinc chloride, tin chloride, ferric chloride, aluminum chloride, and BF3. Catalysts with acids 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; bases 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 tribenzoyloxybismuth; zirconium catalysts such as tetra(ethylacetoacetic acid)zirconium, 1,1'-isopropylidene dichloride zirconium cadhercinate, and tetra(2,4-pentanedione)zirconium, etc.

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

[0223] As a bismuth-based catalyst, there are no particular restrictions as long as it is a bismuth-containing catalyst that promotes the reaction of isocyanates and polyols. Examples of bismuth-based catalysts include: bismuth tri(2-ethylhexanoate), bismuth tribenzoyloxybismuth, bismuth triacetate, bismuth tri(dimethyldithiocarbamate), bismuth hydroxide, bis(trichloroacetic acid)triphenylbismuth(V), tri(4-methylphenyl)oxonylbismuth(V), and triphenylbis(3-chlorobenzoyloxy)bismuth(V).

[0224] From the perspective of catalyst activity, trivalent bismuth compounds are preferred, and more preferably bismuth carboxylate or bismuth compounds represented by the general formula Bi(OCOR)3 (where R is a straight-chain or branched alkyl, cycloalkyl, or a 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, there are no particular restrictions as long as it is a catalyst containing zirconium and a compound that promotes the reaction of isocyanates and polyols. Examples of such products include: cyclopentadienyl zirconium trichloride, decamethylzirconia dichloride, 1,1'-dibutylzirconia dichloride, 1,1'-isopropylidenezirconia dichloride, tetra(2,4-pentanedione)zirconia, tetra(trifluoro-2,4-pentanedione)zirconia, tetra(hexafluoro-2,4-pentanedione)zirconia, zirconium butoxide, zirconium tert-butoxide, zirconium propoxide, zirconium isopropoxide, zirconium ethoxide, bis(ethyl acetoacetic acid) dibutoxyzirconia, tetra(ethyl acetoacetic acid) zirconium, 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, compounds having organic ligands are preferred, more preferably alkoxides, or compounds having an acetylacetonate (2,4-pentanediol) structure. Any of the above-mentioned 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, as a ratio relative to the matrix resin, is preferably in the range of typically 0.0001% by mass or more, especially 0.001% by mass or more and typically 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, it may sometimes be difficult to control the curing reaction.

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

[0230] 6-1-3. Light-curable resins When using a photocurable resin as the 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 stable curing reaction near room temperature, which is the primary operating temperature, is ideal. Therefore, using a photoinitiator for the base resin as a catalyst for curing is an ideal choice.

[0231] Generally, a matrix resin is an active matrix that can generate cations or anions from a base resin using a photoinitiator upon light irradiation. Therefore, it is advisable to select a resin that can cure through these active matrices to produce the base resin.

[0232] Examples of functional groups that react with cations such as protons include epoxy groups and oxocyclic butyl 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 membered rings, such as 3,4-epoxycyclohexylcarboxylate-3,4-epoxycyclohexylmethyl ester and 3,4-epoxy-1-methylhexanecarboxylate-3,4-epoxy-1-methylcyclohexyl 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 an oxetyl group include 2-ethyl-2-oxetyl butyl ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetylbutoxy)hexane. (Note that "(poly)ethylene glycol" and "etc." here refer 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 aforementioned matrix resin, the amount of photoinitiator used for the matrix resin, in terms of its ratio to the polymerizable compound, is preferably in the range of 0.01% by mass or more, particularly 0.1% by mass or more, and typically 1% by mass or less, particularly 0.5% by mass or less. If the amount of photoinitiator used for the matrix resin is too small, curing may sometimes take too long. On the other hand, if the amount of photoinitiator used for the matrix resin is too large, it may sometimes 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. This wavelength difference should be at least 10 nm, and preferably 30 nm. The selection of the photoinitiator for the matrix resin can be roughly predicted based on the absorption wavelength of the initiator.

[0236] 6-2. Photopolymerization initiator The photopolymerization initiator that assists in 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, iodide salts, organothiols, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanones, anthraquinones, ketals, phosphine oxides, sulfones, carbamic acid 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 triggered by light in the visible light range.

[0237] 6-2-1. Titanium eccentricity compounds 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-pentafluorophenyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorophenyl-1-yl)titanium, and bis(cyclopentadienyl)bis(2,6-difluorophenyl-1-yl). Titanium, bis(2,4-difluorophenyl-1-yl)titanium, bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, bis(2,6-difluorophenyl-1-yl)titanium, bis(2,6-difluorophenyl-1-yl)titanium, bis(2,6-difluoro-3-(pyridin-1-yl)-phenyl-1-yl)titanium, etc.

[0239] 6-2-2. Acylphosphine oxide compounds Specific examples of acylphosphine oxide compounds include: monofunctional initiators with only one photobreak point in one molecule and difunctional initiators with two photobreak points 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, and bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide.

[0242] 6-2-3. Oxime ester compounds 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-acetyl oxime) ethyl ketone, 4-(acetoxyimino)-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone, and 4-(acetoxyimino)-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone. Methyl 1-(9-ethyl-6-cyclohexanoyl-9H-carbazole-3-yl)-1-(O-acetyloxime) glutarate, methyl 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetyloxime) glutarate, methyl 1-(O-acetyloxime)-3-methyl-1-(9-ethyl-9H-carbazole-3-yl) ester, etc.

[0243] 6-2-4. Dosage of photopolymerization initiator The above-mentioned photopolymerization initiators can be used individually or in combination or ratio of two or more.

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

[0245] If the amount of photopolymerization initiator is too low, the amount of free radicals generated will be less, which may slow down the photopolymerization process and result in lower recording sensitivity of the holographic recording medium. On the other hand, if the amount of photopolymerization initiator is too high, the free radicals generated by light irradiation may recombine or become heterogeneous, thus sometimes contributing less to photopolymerization and still leading to lower recording sensitivity of the holographic recording medium. When using two or more photopolymerization initiators, it is preferable to ensure that their combined amount meets the above-mentioned range.

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

[0247] 6-3-1. Types of Free Radical Scavengers Examples of reactive groups covalently fixed to the matrix resin include hydroxyl, amino, isocyanate, and thiol groups. Examples of free radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxy radical, and 5-HO-AZADO:5-hydroxy-2-azatricyclo[3.3.1.1] 3,7 ] Decane N-oxygen free radical.

[0248] 6-3-2. Content of free radical scavengers The above-mentioned free radical scavengers can be used individually or in combination or ratio of two or more. The content of the free radical scavenger in the polymerizable composition of the present invention, measured in molar amounts 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 free radical scavenger in the polymerizable 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 tends to decrease, low-polymerization-degree polymers diffuse, and more components 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 tends to decrease, making signal recording impossible. When using two or more free radical scavengers, it is preferable that their total amount meets the above-mentioned range.

[0250] 6-4. Other ingredients 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 include solvents, plasticizers, dispersants, leveling agents, defoamers, and adhesion promoters used in the preparation of polymerizable compositions. Especially in the case of holographic recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, and sensitizers used to control the recording reaction are also examples. Furthermore, examples of other additives that may be needed for property improvement include preservatives, stabilizers, antioxidants, UV absorbers, and light stabilizers. These components can be used individually or in combination or ratios of two or more.

[0252] <Sensitizer> 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 known sensitizer can be selected. Generally, colored compounds such as pigments are used to absorb visible and ultraviolet lasers. In the case of holographic recording media, although the choice depends on the wavelength of the laser used for recording and the type of initiator, 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 systems using blue lasers, compounds described in Japanese Patent Application Publication No. 2000-10277 and Japanese Patent Application Publication No. 2004-198446 are examples. These sensitizers can be used individually or in combination or ratios of two or more.

[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, it should be set to a range of 0.01% by mass or more, particularly 0.1% by mass or more, and typically 10% by mass or less, particularly 5% by mass or less, relative to the ratio of the photopolymerization initiator described in 6-2 above. If the amount of sensitizer used is too small, the initial 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] <Plasticizers> 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: phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and di(undecyl) phthalate; adipates such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate; sebacate such as dioctyl sebacate and dibutyl sebacate; phosphates such as tricresyl phosphate; citrates such as acetyl tributyl citrate; trimellitic acid 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] Plasticizers 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)dicarbamate, [4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl]dicarbamate bis(2,2,2-trifluoroethyl) ester, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononylbutyl ester, and 2,2,2-trifluoroethylphenyl ester.

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

[0260] Leveling agent Leveling agents can be used in the polymerizable compositions 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, fluorinated compounds, etc. Any one of these can be used alone, or two or more can be used in any combination and ratio.

[0261] <Chain transfer agent> Chain transfer agents can be used in the polymerizable compositions of the present invention. Examples of chain transfer agents include: phosphonates such as sodium phosphite and sodium hypophosphite; thiols such as mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, and thiophene; aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; terpenes such as terpinene, α-terpinene, β-terpinene, and γ-terpinene; and 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, 1,4-heptadiene, 1,4-hexadiene, and 2- Non-conjugated dienes such as methyl-1,4-pentadiene, 3,6-nonadien-1-ol, and 9,12-octadecadienol; linolenic acids such as linolenic acid, gamma-linolenic acid, methyl linolenic acid, ethyl linolenic acid, isopropyl linolenic acid, and linolenic anhydride; linoleic acids such as linoleic 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 typically 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, the total amount of them should satisfy the above range.

[0263] 6-5. Composition ratio of each component in a polymeric composition The content of each component in the polymeric composition of the present invention is arbitrary, as long as it does not violate the spirit of the present invention. The proportions of each component shown below are preferably within the following ranges based on the molar 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 keeping the content of the polymeric compound above the aforementioned lower limit, sufficient diffraction efficiency can be obtained in the holographic recording medium; by keeping the content of the polymeric compound below the aforementioned upper limit, compatibility with the resin matrix in the recording layer is tended to be 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 polymerizable composition of the present invention, the combined content of these is typically 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, and typically 99.9% by mass or less, preferably 99% by mass or less. By setting this content to the above-mentioned lower limit or above, a recording layer is easily formed.

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

[0267] Furthermore, in this polymerizable composition, the content of the urethane 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. Furthermore, it is preferable to use 0.003% by mass or more.

[0268] The total amount of other components besides those mentioned above should be 30% by mass or less, preferably 15% by mass or less, and more preferably 5% by mass.

[0269] 6-6. Methods for manufacturing polymeric compositions In this invention, the method for manufacturing the 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 mixed in any combination and in any order.

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

[0271] Each liquid is preferably dehydrated and degassed. If dehydration and degassed inadequately, air bubbles may be generated during the fabrication of the holographic recording medium, resulting in an ununiform recording layer. Heating and depressurization can also be performed during dehydration and degassed processes, as long as the components are not damaged.

[0272] In the manufacture of the polymerizable composition of liquid A and liquid B, it is preferable to carry out the process just before the holographic recording medium is formed. At this time, mixing techniques based on existing methods can also be used. Furthermore, during the mixing of liquid A and liquid B, degassing may be performed as needed to remove residual gases. Further, liquid A and liquid B are preferably subjected to 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, if necessary, a support or other layers. Typically, a holographic recording medium has a support, on which the recording layer or other layers are stacked to form the holographic recording medium. However, if the recording layer or other layers have the strength or durability required by the medium, the holographic recording medium may not have a support. 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 typically recorded in the form of holography. As described in the recording method section below, a portion of the polymeric compound (hereinafter referred to as a polymeric monomer) contained in this 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 resulting from the reaction of a polymer, etc.

[0276] The thickness of the recording layer is not particularly limited, and can be appropriately determined by considering the recording method, etc. Preferably, it is 1 μm or more, more preferably 10 μm or more, and further preferably 1 cm or less, more preferably 3 mm or less. By setting the thickness of the recording layer to the lower limit or above, the selectivity of each hologram can often be improved, and the degree of multiple recording can be enhanced when multiple recordings are performed on a holographic recording medium. By setting the thickness of the recording layer to the upper limit or below, the recording layer can often be uniformly shaped, enabling multiple recordings with uniform diffraction efficiency and a high S / N ratio for each hologram.

[0277] Regarding the shrinkage rate of the recording layer due to exposure during information recording and reproduction, considering the reproducibility of the recording, it is preferably 0.25% or less.

[0278] 6-7-2. Support There are no particular restrictions on the details of the support body, as long as it has the strength and durability required for holographic recording media, any support body can be used. The shape of the support is also unrestricted, and it is usually formed as a plate or a membrane. There are no restrictions on the materials used to make the support; they can be transparent or opaque.

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

[0280] If we take opaque materials as examples of support materials, we can include: metals such as aluminum, and materials made by coating the above-mentioned transparent support with metals such as gold, silver, aluminum, or dielectrics such as magnesium fluoride and zirconium oxide.

[0281] There are no particular limitations 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, advantages such as increased light transmittance and reduction in the weight or cost of the holographic recording medium can be obtained.

[0282] Surface treatments can also be applied to the surface of the support. These surface treatments are 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 a primer coating on the support. Examples of primer coating compositions include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc.

[0283] Surface treatments of the support can also be performed for purposes other than improving adhesion. Examples include reflective coating treatments that form reflective coatings using metals such as gold, silver, or aluminum; and dielectric coating treatments that form dielectric layers such as magnesium fluoride or zirconium oxide. These layers can be single layers or two or more layers.

[0284] These surface treatments can also be designed to control the permeability of gas or moisture to the substrate. For example, by making the support sandwiching the recording layer also suppress 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 shall be made transparent so that active energy rays (excitation light, reference light, reproduction light, etc.) can pass through.

[0286] In the case of a holographic recording medium having supports on one or both sides of the recording layer, transmissive or reflective holography can be recorded. Furthermore, when a support with reflective properties is used on one side of the recording layer, reflective holography can be recorded.

[0287] Patterning for data addresses can also be applied to the support. There are no limitations on the patterning method in this case; for example, the pattern can be formed on the support itself, on the reflective layer described below, or by combining these methods.

[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 formulation 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. In addition, it can also be formed 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 surface of the support, but it is generally preferred to be located between the support and the recording layer. As a reflective layer, any known reflective layer can be used, such as a thin film of metal.

[0291] 6-7-5. Anti-reflective film For any type of holographic recording medium, whether transmissive or reflective, an anti-reflective film can be placed on the sides where the information light, reference light, and reproduction light are incident and emitted, or between the recording layer and the support. The anti-reflective film improves light utilization efficiency and suppresses noise generation. As an antireflective film, any known antireflective film can be used.

[0292] 6-7-6. Methods for Manufacturing Holographic Recording Media The method for manufacturing the holographic recording medium of the present invention is not limited. For example, it can be manufactured by coating the polymeric composition of the present invention onto a support in a solvent-free manner 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 the recording layer, especially in the case of forming a thicker recording layer, a method of molding in a mold can be used, or a method of coating onto a release film and then stamping the mold can be used. Alternatively, a coating liquid can be prepared by mixing the polymeric composition of the present invention with a solvent or additives, and this coating liquid can be coated onto a support and dried to form the recording layer. In this case, any coating method can be used, for example, the same method as described above.

[0294] There are no restrictions on the solvent used in the coating solution. Generally, a solvent with sufficient solubility for the components used, providing good film properties, and not penetrating the support such as the resin substrate is preferred. A single solvent can be used, or two or more solvents can be used in any combination and ratio. Furthermore, there are no restrictions on the amount of solvent used. However, considering coating efficiency and operability, a coating solution with a solid content concentration of approximately 1 to 100% by mass is preferred.

[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 furfuryl alcohol; ketol-alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; ether solvents such as tetrahydrofuran and dioxane; halogen solvents such as dichloromethane, dichloroethane, and chloroform; cellosol solvents such as methyl cellosol, ethyl cellosol, butyl cellosol, methyl cellosol acetate, and ethyl cellosol 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 acetate. Solvents include: propylene glycol solvents such as esters 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 acetoacetate, 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, tert-butylcyclohexane, and cyclooctane; or mixtures of these solvents.

[0296] Methods for manufacturing holographic recording media include, for example, the following: 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, curing it by thermal polymerization to form a recording layer; and a method of manufacturing by coating a liquid polymeric composition onto a support, curing it by photopolymerization to form a recording layer.

[0297] The holographic recording medium produced in this way can take the form of a self-supporting flat plate or disc, and can be used in three-dimensional image display devices, diffractive optical elements, large-capacity storage devices, and other applications. In particular, the holographic recording medium of the present invention, which uses 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. Uses of Holographic Recording Media <Applications of High-Capacity Memory> The writing (recording) and reading (reproducing) of information in the holographic recording medium of the present invention are both performed by light irradiation.

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

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

[0301] In the case of volumetric holographic reconstruction of the recording layer, a predetermined reconstruction light (usually a reference light) is irradiated onto the recording layer. The irradiated reconstruction light diffracts according to the aforementioned interference fringes. This 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 reconstructed light, and the reference light can be arbitrary depending on their respective applications, and can be either in 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 dye lasers with excellent monochromaticity and directionality, such as dye lasers.

[0303] There are no restrictions on the amount of irradiation of the object light, the reproduction light, and the reference light; as long as it is within the range that allows for recording and reproduction, the amount of irradiation can be arbitrary. When the irradiation amount 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 amount is very high, the composition of the recording layer (the composition of the polymeric composition of the present invention) may deteriorate. Therefore, the object light, the reproduction light, and the reference light are typically 0.1 J / cm², depending on the composition of the polymeric composition of the present invention used to form the recording layer, the type and amount of the photopolymerization initiator, etc. 2 Above and 20J / cm 2 Irradiate the following area.

[0304] As holographic recording methods, there are coaxial polarization holographic recording methods, reference light incident angle multiplexing 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] <Applications of AR Glasses Light Guide Plate> The holographic recording medium of the present invention, in the same way as the above-described use of a large-capacity memory, records volumetric holography.

[0306] For volumetric holography recorded on a recording layer, a predetermined reconstructed light is irradiated onto the recording layer. The irradiated reconstructed light diffracts according to the aforementioned interference fringes. Even if the wavelength of the reconstructed light differs from the wavelength of the recording light, diffraction still occurs as long as the Bragg condition is satisfied with the interference fringes. Therefore, if corresponding interference fringes are pre-recorded based on the wavelength and incident angle of the desired diffracted reconstructed light, diffraction can be achieved over a wide wavelength range, 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 reproduced light, the reproduced light incident from the outside of the holographic recording medium can be guided to the inside of the holographic recording medium, or the reproduced light guided inside the holographic recording medium can be reflected, split, expanded, or reduced. Thus, the reproduced light guided inside the holographic recording medium can be emitted to the outside of the holographic recording medium, thereby expanding the viewing angle of the AR glasses.

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

[0309] There are no restrictions on the amount of irradiation of the object light, the reproduction light, and the reference light; as long as it is within the range that allows for recording and reproduction, the amount of irradiation can be arbitrary. When the irradiation amount 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 amount is very high, the composition of the recording layer (the composition of the polymeric composition of the present invention) may deteriorate. Therefore, the object light, the reproduction light, and the reference light are typically 0.1 J / cm² depending on the composition of the polymeric composition of the present invention used to form the recording layer, the type of photopolymerization initiator, and the mixing amount. 2 Above and 20J / cm 2 Irradiate the following area.

[0310] 6-8. Performance Indicators of Holographic Recording Media The performance of a holographic recording medium is quantified by the total Δn, calculated from the sum of the diffraction efficiencies of multiple recordings. In the case of transmission holography, the diffraction efficiency 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] Total Δn = ∑Δn

[0312] Here, η is the diffraction efficiency, T is the medium thickness, 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 storage, a higher total Δn means that more information can be recorded per unit volume, which is preferable. 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 preferable. [Example]

[0314] The present invention will be further described in detail below through embodiments. The present invention is not limited to the following embodiments without departing from its spirit.

[0315] The following sections provide a detailed description of the synthetic methods for each compound, including its chemical formula and the synthetic process.

[0316] [Ingredients Used] The raw materials used in the compositions in the examples and comparative examples are shown below.

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

[0318] <Polyols> PLACEL PCL-205U: Polycaprolactone Diol (Molecular Weight 530) (Manufactured by Daicel Corporation) PLACEL PCL-305: Polycaprolactone Triol (Molecular Weight 550) (Manufactured by Daicel Corporation)

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

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

[0321] <Carbamate Polymerization Catalyst> • Octanoic acid solution of bismuth tris(2-ethylhexanoate) (active ingredient content 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 are produced by the following synthesis method.

[0323] [Chemistry 21]

[0324] Dissolve 20g of dibenzothiophene in 300mL of THF, cool to 0°C, and simultaneously add 74.6mL of a 1.6M n-butyllithium hexane solution. Heat to 20°C and stir for 2 hours. Cool the resulting brown reaction solution to -40°C and add 3.8g of sulfur (powder, manufactured by Wako Pure Chemicals). After stirring at -40°C for 30 minutes, add 5mL of water to the reaction solution to terminate the reaction. The obtained solution was concentrated using an evaporator, and the obtained solid was washed with 100 mL of toluene for 30 minutes. The yellow solid was then separated by filtration to produce 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 hydrochloric acid, and 1 equivalent sodium hydroxide aqueous solution, and then concentrated. Recrystallization from hexane yielded 9.4 g (40% yield) of compound S-2.

[0326] Add several mL of deuterated chloroform to an appropriate amount of compound S-2 (approximately 10 mg) and dissolve it. If there are insoluble components, filter through a cotton plug. Transfer the solution to a dedicated sample tube and cap it. Using this sample tube, determine the resonance state of hydrogen in a 400 MHz nuclear magnetic resonance (NMR) instrument. Assign each resonance line to hydrogen of the compound to confirm the acquisition of the target analyte. The measurement data are shown below. Measurements were also performed similarly for the target analytes described below, confirming their acquisition. The measurement data are shown below. 1 H NMR(400MHz, 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 prepared 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 complete, 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 over sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to obtain 9.7 g (97% yield) of compound S-3.

[0331] The NMR data for compound S-3 are shown below. 1 H-NMR(400M Hz, CDCl3) δ8.31-8.29(m,2H),8.15(d,J=9.5Hz,2H),7.99-7.97(m,2H),7.53-7.50(m ,6H),7.39(t,J=3.5Hz,2H), 4.78(t,J=4.8Hz,2H), 3.51(d,J=4.8Hz,4H), 3.27(s,4H).

[0332] Under a nitrogen atmosphere, compound S-3 (3.0 g), sodium tert-butoxide (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 solution was injected into 50 mL of water, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to obtain 1.9 g (yield 51%) of compound S-4.

[0333] The NMR data for compound S-4 are shown below. 1 H NMR(400MHz, 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 2-isocyanoethyl 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 silica gel short-path column. The resulting solution was concentrated to a total volume of 10 g at temperatures below 30 °C. This solution was added dropwise to 100 mL of ice-cooled methanol, and the mixture was 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. 1 H NMR (400MHz, 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,7.36(Ar,1H),7.44(Ar,5H),7.52(Ar,2H),7.79(Ar,4H),7.94(Ar,2H)

[0336] <The 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 DURANATE (registered trademark) TSS-100. In addition, PLACEL PCL-205U: 1.73g and PLACEL PCL-305: 0.74g were mixed (PLACCELPCL-205U:PLACCEL PCL-305 = 70:30 (mass ratio)) and 0.2mg of tri(2-ethylhexanoic acid)bismuth in octanoic acid solution was dissolved to prepare solution B.

[0337] After degassing solutions A and B separately at room temperature or 45°C under reduced pressure for 2 hours, 2.39g of solution A and 2.11g of solution B are stirred and mixed, and then further degassed under vacuum for several minutes. Next, the above-mentioned mixture, which had been degassed under vacuum, was poured onto a glass slide with 0.5 mm thick spacers placed at opposite ends. Another glass slide was then placed on top, and the perimeter was fixed using clamps. The slide was then 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 that serve as the outer cover.

[0338] The holographic recording medium is a mixture of isocyanate groups in solution A and isocyanate reactive groups in solution B in a ratio 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] Using the holographic recording medium of the prepared evaluation sample, the holographic recording and the evaluation of the holographic recording performance of the holographic recording medium are carried out in the order described below.

[0340] Holographic recording uses a semiconductor laser with a wavelength of 405nm. Figure 1 The exposure apparatus shown has an exposure power density of 10.2 mW / cm² per beam. 2 Holographic recording of a two-beam plane wave was performed. The medium was rotated from -22.5° to 22.5°, and multiple angular recordings were performed at the same location. The diffraction efficiency of each multiple recording was measured. Δn was calculated based on the obtained diffraction efficiency, and the sum of the total diffraction efficiencies in the multiple recordings was taken as the total Δn. The following is a detailed explanation.

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

[0342] like Figure 1 As shown, light with a wavelength of 405 nm is split by a polarizing beam splitter (PBS in the figure) and made to cross 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 beam splitting is made perpendicular to the plane containing the two intersecting beams for illumination.

[0343] After holographic recording, a light source (V05-LHP151 manufactured by Melles Griot: “L2” in the figure) that can obtain a wavelength of 633nm using a He-Ne laser is used to illuminate the holographic recording medium at an angle of 50.7°. The diffracted light is detected using a photodiode and a photodetector 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 by which the sample is moved relative to the optical axis (the angle between the two beams, i.e., from the optical axis) Figure 1 The angle between the inner angle bisector of the intersection of the incident light from mirrors M1 and M2 and the sample normal was moved from -22.5° to 22.5° in increments of 0.3°, and 151 multiple recordings were performed.

[0345] After multiple recordings, the LED unit (1 in the figure, center wavelength 405nm) is lit for a certain period of time to consume any remaining initiator and monomer. This step is called post-exposure. The LED power is set to 100mW / cm². 2 And with a cumulative energy of 12 J / cm 2 Irradiation is performed in this manner.

[0346] The diffraction efficiency of holography is given by the ratio of the diffracted light intensity to the sum of the transmitted light intensity and the diffracted light intensity. Illumination Figure 1The diffraction efficiency (wavelength 405 nm) from mirror M1 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 all multiple records was taken as the total Δn.

[0347] [Number 2] Total Δn = ∑Δn

[0348] Here, η is the diffraction efficiency, T is the medium 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 for multiple evaluations, such as increasing or decreasing the initial irradiation energy and the total irradiation energy, to explore the conditions that would deplete the polymerizable monomers (approximately balancing the total Δn during multiple recordings), thereby maximizing the total Δn. The obtained maximum value was then set as the total Δn for that medium.

[0350] (Determination 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 sample for evaluation before recording. In addition, the transmittance after recording is determined by measuring the ratio of the transmitted light power to the incident light power of the sample after post-exposure evaluation of holographic recording.

[0351] (Record the measurement of haze) Evaluation samples that underwent holographic recording and post-exposure were used, and the haze value for white light was measured using a haze meter NDH 7000SPII manufactured by Nippon Denshoku Kogyo Co., Ltd. (JIS K7136). In addition, the ratio of this haze value to the total Δn mentioned above (haze% / total Δn) is calculated. The lower the ratio, the better the balance between diffraction efficiency and transparency.

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

[0353] [Chemistry 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 by silica gel column chromatography (hexane / ethyl acetate) to give 12.4 g (88% yield) of compound S-5.

[0355] The NMR data for compound S-5 are shown below. 1 H NMR (400MHz, 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 (3g), dibenzothiophene-4-boric acid (4.5g), and potassium phosphate (5.5g) were suspended in 20mL toluene, 10mL ethanol, and 10mL water, and degassed by purging with nitrogen. 138mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was purged for another 10 minutes. The reaction solution was heated under 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 0.4g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After diatomaceous earth filtration, the mixture was concentrated, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 4.4g of crude compound S-6.

[0357] The NMR data for compound S-6 are shown below. 1 H NMR (400MHz, 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 was purified by silica gel column chromatography (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. 1 H NMR(400MHz,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 2-isocyanoethyl 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 0.3 g of 2-isocyanoethyl 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 extraction with 50 mL of chloroform. The resulting organic layer was dried over magnesium sulfate and concentrated at below 30°C. The crude product obtained by concentration was purified using a silica gel column (hexane / ethyl acetate) to obtain 3.6 g (62% yield) of compound M-2.

[0361] The NMR data for compound M-2 are shown below. 1 H NMR(400MHz,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),6.1 0(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 prepared by the following synthetic method.

[0364] [Chemistry 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 by silica gel column chromatography (hexane / ethyl acetate) to give 26.5 g (96% yield) of compound S-5. The NMR data of the obtained compound S-5 are as described above.

[0366] Compound S-5 (9 g), dithioxanthracene-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 layers were combined with another batch that had undergone the same reaction, concentrated, and the crude product was purified by silica gel column chromatography (heptane·ethyl acetate) to obtain 16 g (66% yield) of compound S-8.

[0367] The NMR data for compound S-8 are shown below. 1 H NMR (400MHz, 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 by silica gel column chromatography (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. 1 H NMR(400MHz,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. 1.1 g of 2-isocyanoethyl acrylate was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.5 g of 2-isocyanoethyl 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 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 silica gel column (hexane / ethyl acetate) to give 5.1 g (70% yield) of compound M-3.

[0371] The NMR data for compound M-3 are shown below. 1 H NMR(400MHz, 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 prepared by the following synthetic method.

[0374] [Chemistry 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 by silica gel column chromatography (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. 1 H NMR (400MHz, 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-boric 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, and nitrogen was purged for another 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 and stirred for 30 minutes. After diatomaceous earth filtration, the solution was concentrated, and the crude product was purified by silica gel column chromatography (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(400MHz, 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 by silica gel column chromatography (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. 1 H NMR(400MHz,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 2-isocyanoethyl 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 2-isocyanoethyl 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 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 silica gel 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(400MHz,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 prepared by the following synthetic method.

[0385] [Chemistry 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 by silica gel column chromatography (hexane / ethyl acetate) to give 35 g (94% yield) of compound S-10. The NMR data of compound S-10 are as described above.

[0387] Compound S-10 (29.2 g), dithioxanthracene-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 by silica gel column chromatography (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 (400MHz, 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 further 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 over anhydrous magnesium sulfate and concentrated. The crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz, 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. 1.1 g of 2-isocyanoethyl acrylate was then added to the solution, and the reaction was carried out at room temperature for 50 hours. After the reaction was complete, the solution was concentrated at a temperature below 30 °C, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.6 g (80% yield) of compound M-5.

[0392] The NMR data for compound M-5 are shown below. 1H NMR(400MHz,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 prepared by the following synthetic method.

[0395] [Chemistry 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. 1 H NMR (400MHz, 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 by silica gel column chromatography (hexane / ethyl acetate) to give 5.5 g (78% yield) of compound S-16.

[0399] The NMR data for compound S-16 are shown below. 1 H NMR(400MHz,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. 0.98 g of 2-isocyanoethyl acrylate was then added to the solution, and the reaction was carried out at 30 °C for 30 hours. After the reaction was complete, the solution was concentrated at a temperature below 30 °C, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 2.0 g (70% yield) of compound M-6.

[0401] The NMR data for compound M-6 are shown below. 1H NMR(400MHz, 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 prepared by the following synthetic method.

[0404] [Chemistry 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 give 1.3 g (76% yield) of compound S-17.

[0406] The NMR data for compound S-17 are shown below. 1 H NMR(400MHz, 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. 1 H NMR (400MHz, 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. 1.0 g of 2-isocyanoethyl acrylate 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 the mixture was extracted 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 by silica gel column chromatography (hexane / ethyl acetate) to give 3.4 g (72% yield) of compound M-7.

[0410] The NMR data for compound M-7 are shown below. 1 H NMR(400MHz,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 prepared by the following synthetic 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 added to the solution in three portions, 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 by silica gel column chromatography to obtain 1.85 g (68% yield) of compound S-19.

[0415] The NMR data for compound S-19 are shown below. 1 H NMR(400MHz,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, and nitrogen was purged for another 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 1N NaOH aqueous solution. Further washing with water and brine was performed, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified by silica gel column chromatography to obtain 1.8 g (89% yield) of compound S-20.

[0417] The NMR data for compound S-20 are shown below. 1 H NMR(400MHz,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 2-isocyanoethyl 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 silica gel 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 for compound M-8 are shown below. 1 H NMR(400MHz,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,1 0H),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 prepared by the following synthetic 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 1N sodium hydroxide solution, and then washed with brine. The resulting solution was dried over anhydrous magnesium sulfate and concentrated, and then purified by silica gel column chromatography (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. 1 H NMR(400MHz,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 added to the solution in three portions, and the reaction was allowed to proceed for 7 hours at room temperature. 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 by silica gel column chromatography (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. 1 H NMR(400MHz,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, and nitrogen was purged for another 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 1N sodium hydroxide aqueous solution. Further washing with water and brine was performed, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz,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 2-isocyanoethyl 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 silica gel 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-cooled 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 for compound M-9 are shown below. 1H NMR(400MHz,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 prepared by the following synthetic 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 added to the solution in three portions, and the reaction was carried out at room temperature for 12 hours. The reaction was terminated by adding water, and the organic layer was washed with 0.1 N hydrochloric acid and water after separation. The resulting solution was dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz,CDCl3,δ,ppm)2.46(t,OH,1H),3.16(m,CH2,4H),3.68(d,CH2,2H),4.32(s,CH2,2 H),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, and nitrogen was purged for another 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 1N sodium hydroxide aqueous solution. Further washing with water and brine was performed, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz,CDCl3,δ,ppm)1.99(brs,OH,1H),2.67-2.79(m,CH2,4H),3.17(brd,CH2,2H),3.86(brs,CH 2,2H),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 2-isocyanoethyl 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 silica gel 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 for compound M-10 are shown below. 1H NMR(400MHz,CDCl3,δ,ppm)2.68(brs,CH2,4H),3.00+3.22(brs+m,CH2,2H),3.7 6(brs,CH2,2H),3.82(brs,CH2,2H),3.92+4.07(brs+t,CH2,2H),4.48(brt,NH,1 H),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 prepared by the following synthetic 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 further with 1N sodium hydroxide solution, and then washed with brine. The resulting solution was dried over anhydrous magnesium sulfate and concentrated, and then purified by silica gel column chromatography (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. 1 H NMR(400MHz,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. Further washing with brine and water followed by drying with anhydrous magnesium sulfate was performed. After concentration, the crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz,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 dried using anhydrous magnesium sulfate. The crude product was concentrated and purified by silica gel column chromatography (dichloromethane, ethyl acetate) to obtain 1.7 g (87% yield) of compound S-28.

[0448] The NMR data for compound S-28 are shown below. 1 H NMR(400MHz,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, and nitrogen was purged for another 10 minutes. The reaction solution was heated under nitrogen atmosphere and stirred under reflux for 4 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with 1N sodium hydroxide aqueous solution. Further washing with water and brine was performed, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified by silica gel column chromatography (dichloromethane, ethyl acetate) to obtain 1.7 g (84% yield) of compound S-29.

[0450] The NMR data for compound S-29 are shown below. 1 H NMR(400MHz,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+br s,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 2-isocyanoethyl 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 silica gel 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-cooled 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 for compound M-11 are shown below. 1H NMR(400MHz,CDCl3,δ,ppm),3.21-3.35(br,CH2,6H),3.41(q,CH2,2H),3.77+3.86(b rs+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 prepared by the following synthetic method.

[0455] [Chemistry 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 dichloromethane solution containing 300 mg of acryloyl chloride was added to this solution, and the mixture was stirred for 2 hours. After the reaction was complete, 10 mL of a saturated sodium bicarbonate aqueous solution was added, and the mixture was extracted twice with 50 mL of dichloromethane. The organic layer was dried over sodium sulfate, filtered, and concentrated. The crude product was purified using a silica gel column (hexane / ethyl acetate) to obtain 770 mg (54% yield) of compound M-12.

[0456] The NMR data for compound M-12 are shown below. 1H NMR(400MHz, 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,1 H),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 prepared by the following synthetic method.

[0458] [Chemistry 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 an ethyl acetate / hexane mixture, 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. 1 H NMR (400MHz, 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, and nitrogen was purged for another 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 the mixture was stirred for 30 minutes. After diatomaceous earth filtration, the mixture was concentrated, and the crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz,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 min 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 by silica gel column chromatography (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. 1 H NMR (400MHz, 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. 0.9 g of 2-isocyanoethyl acrylate 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 by silica gel column chromatography (hexane / ethyl acetate) to give 3.4 g (78% yield) of compound M-13.

[0466] The NMR data for compound M-13 are shown below. 1 H NMR(400MHz,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 prepared by the following synthetic 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 by silica gel column chromatography (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. 1 H NMR(400MHz, 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), dithioxanthracene-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 under a nitrogen atmosphere and stirred for 12 hours. 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 by silica gel column chromatography (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. 1 H NMR (400MHz, 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 by silica gel column chromatography (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. 1 H NMR(400MHz,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. 0.63 g of 2-isocyanoethyl acrylate was added to this solution, and the reaction was carried out at room temperature. After 24 hours, an additional 0.5 g of 2-isocyanoethyl 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 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 silica gel column (hexane / ethyl acetate) to give 1.0 g (24% yield) of compound M-14.

[0476] The NMR data for compound M-14 are shown below. 1 H NMR(400MHz,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(d d,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 prepared by the following synthetic method.

[0478] [Chemistry 36]

[0479] 6.7 g of o-vanillin and 5.0 g of 2-aminobenzenethiol 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 48 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 5.4 g (53% yield) of compound S-36.

[0480] The NMR data for compound S-36 are shown below. 1H NMR (400MHz, CDCl3, δ, ppm) 3.95 (s, 6H), 6.90 (dd, 1H), 6.99 (dd, 1H), 7.32 (dd, 1 H),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 by silica gel column chromatography (hexane / ethyl acetate) to obtain 2.9 g (59% yield) of compound S-37.

[0482] The NMR data for compound S-37 are shown below. 1 H NMR(400MHz, 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 by silica gel column chromatography (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(400MHz, 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(d d,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. 0.65 g of 2-isocyanoethyl acrylate 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 the mixture was extracted 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 by silica gel column chromatography (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. 1 H NMR (400MHz, 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 prepared by the following synthetic 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. 1 H NMR (400MHz, 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. 1 H NMR(400MHz,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 dioxane 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, and nitrogen was purged for another 10 minutes. The reaction solution was heated under 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 the mixture was stirred for 30 minutes. After diatomaceous earth filtration, the mixture was concentrated, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 4.7 g of crude compound S-41.

[0494] The NMR data for compound S-41 are shown below. 1 H NMR(400MHz, 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 was purified by silica gel column chromatography (hexane / ethyl acetate) to give 5.5 g of compound S-42.

[0496] The NMR data for compound S-42 are shown below. 1 H NMR(400MHz,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. 0.83 g of 2-isocyanoethyl acrylate 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 the mixture was extracted 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 by silica gel column chromatography (hexane / ethyl acetate) to give 2.8 g (45% yield) of compound M-16.

[0498] The NMR data for compound M-16 are shown below. 1H NMR(400MHz,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 prepared by the following synthetic 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 by silica gel column chromatography (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. 1 H NMR (400MHz, 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, and nitrogen was purged for another 10 minutes. The reaction solution was heated under 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 and stirred for 30 minutes. After diatomaceous earth filtration, the solution was concentrated, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 15 g of crude compound S-44.

[0504] The NMR data for compound S-44 are shown below. 1 H NMR(400MHz, 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 using 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 further stirring for 2 hours, the precipitate was separated by filtration. The obtained solid was redissolved in 80 mL of dichloromethane, passed through a silica gel short-pass column, and concentrated to give 3.8 g (73% yield) of compound S-45.

[0506] The NMR data for compound S-45 are shown below. 1H NMR(400MHz, 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. 0.68 g of 2-isocyanoethyl acrylate was added to this solution, and the reaction was carried out at room temperature for 50 hours. After the reaction was complete, the reaction solution was concentrated at a temperature below 30 °C, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.0 g (80% yield) of compound M-17.

[0508] The NMR data for compound M-17 are shown below. 1 H NMR(400MHz,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(A r,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 prepared by the following synthetic 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 obtained was purified by silica gel column chromatography (hexane / ethyl acetate) to give 15.5 g (68% yield) of compound S-46.

[0512] The NMR data for compound S-46 are shown below. 1 H NMR(400MHz, 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,O H,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. 0.60 g of 2-isocyanoethyl acrylate 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 the mixture was extracted 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 by silica gel column chromatography (hexane / ethyl acetate) to give 1.3 g (36% yield) of compound M-18.

[0514] The NMR data for compound M-18 are shown below. 1 H NMR(400MHz,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 prepared by the following synthetic method.

[0516] [Chemistry 40]

[0517] 10 g of 3,6-dibromo-9H-carbazole, 14.7 g of dibenzothiophene-4-boric 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 purged for another 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. 1 H NMR(400MHz, 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. 1 H NMR (400MHz, 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 by silica gel column chromatography (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. 1 H NMR(400MHz, 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. 0.37 g of 2-isocyanoethyl acrylate was added to this 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 over magnesium sulfate and concentrated at a temperature below 30 °C. The crude product obtained by concentration was purified by silica gel column chromatography (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. 1 H NMR(400MHz, 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),5.6 8(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 prepared by the following synthetic method.

[0526] [Chemistry 41]

[0527] Compound S-11 (3.5 g) obtained in Example 4, 5-methyl-1,3,4-thiadiazole-2-thiol (0.84 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 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 by silica gel column chromatography (hexane / ethyl acetate) to give 3.1 g (74% yield) of compound S-50.

[0528] The NMR data for compound S-50 are shown below. 1 H NMR(400MHz, 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. 0.82 g of 2-isocyanoethyl acrylate was added to this 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 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 by silica gel column chromatography (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 (400MHz, 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 prepared by the following synthetic method.

[0532] [Chemistry 42]

[0533] Compound S-11 (5.0 g) obtained in Example 4, 5-chloro-2-mercaptobenzothiazole (1.81 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 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 by silica gel column chromatography (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. 1 H NMR(400MHz, CDCl3, δ, ppm)3.23(d,2H),3.43(d,2H),3.63(d,2H),3.68(s,2H),5.0 5(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. 0.93 g of 2-isocyanoethyl acrylate was added to this 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 by silica gel column chromatography (hexane / ethyl acetate) to give 1.9 g (37% yield) of compound M-21.

[0536] The NMR data for compound M-21 are shown below. 1 H NMR(400MHz,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 prepared by the following synthetic 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. 1 H NMR(400MHz, 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 min 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 by silica gel column chromatography (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. 1 H NMR(400MHz,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. 0.5 g of 2-isocyanoethyl acrylate 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 the mixture was extracted 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 by silica gel column chromatography (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. 1 H NMR(400MHz,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 prepared by the following synthetic 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 further added, and the reaction was carried out under reflux for 1 hour. The resulting solution was washed with water and dried over anhydrous magnesium sulfate. After concentration, the crude product was purified by silica gel column chromatography (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. 1 H NMR(400MHz,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 purged for another 10 minutes. The reaction solution was heated under nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, the solution was extracted with ethyl acetate and washed with 1N sodium hydroxide aqueous solution. Further washing with water and brine was performed, and the organic layer was dried with anhydrous magnesium sulfate. The solution was concentrated, and the crude product was purified by silica gel column chromatography (dichloromethane, ethyl acetate) to obtain 2.5 g (75% yield) of compound S-55.

[0550] The NMR data for compound S-55 are shown below. 1H NMR(400MHz,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),4.2 6+4.32(s+brs,CH2,2H),4.92+5.09(brs+t,NH,1H),6.75+6.86(Ar,1H),7.0 9-7.18(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 2-isocyanoethyl 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 silica gel 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-cooled 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 for compound M-23 are shown below. 1 H NMR(400MHz,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,1 H),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 prepared by the following synthetic method.

[0554] [Chemistry 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 this 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 concentrated. The crude product obtained by concentration was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 10 g (49% yield) of compound S-56.

[0556] The NMR data for compound S-56 are shown below. 1 H NMR (400MHz, 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 2-isocyanoethyl 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 0.4 g of 2-isocyanoethyl acrylate 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 by silica gel column chromatography (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. 1 H NMR (400MHz, 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 prepared 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 by silica gel column chromatography (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. 1 H NMR(400MHz, 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-boric 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 purged for another 10 minutes. The reaction solution was heated under 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 diatomaceous earth filtration and concentration, the crude product was purified by silica gel column chromatography (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(400MHz, 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 over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified by silica gel column chromatography (hexane / ethyl acetate) to give 1.5 g (45% yield) of compound M-25.

[0567] The NMR data for compound M-25 are shown below. 1 H NMR (400MHz, 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 prepared by the following synthetic method.

[0570] [Chemistry 47]

[0571] Compound S-57 (2.0 g) obtained in Comparative Example 2, 2.7 g of dithioxanthracene-1-boric 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 another 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 and stirred for 30 minutes. After diatomaceous earth filtration and concentration, the crude product was purified by silica gel column chromatography (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. 1 H NMR (400MHz, 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 2-isocyanoethyl 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 300 mg of 2-isocyanoethyl acrylate 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 by silica gel column chromatography (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 (400MHz, 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 prepared 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 over sodium sulfate and concentrated. The crude product obtained by concentration was purified by silica gel column chromatography (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. 1 H NMR (400MHz, 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-boric 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, and nitrogen was purged for another 10 minutes. The reaction solution was heated under 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 0.5 g of activated carbon was added to the obtained organic layer and stirred for 30 minutes. After diatomaceous earth filtration and concentration, the crude product was purified by silica gel column chromatography (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. 1 H NMR (400MHz, 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 2-isocyanoethyl 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 400 mg of 2-isocyanoethyl acrylate 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 by silica gel column chromatography (hexane / ethyl acetate) to give 1.1 g (33% yield) of compound M-27.

[0583] The NMR data for compound M-27 are shown below. 1H NMR(400MHz, 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]

[0586] In the production of holographic recording media, the molar concentrations of polymerizable monomers, photopolymerization initiators, and additives were set to fixed values. Only the types of polymerizable monomers were changed to produce holographic recording media, which were then evaluated (Table 1). As shown in Table 1, in Comparative Examples 1 to 4, where the polymeric monomers used have three high-refractive-index regions with the same structure, the haze % / total Δn is 3.6 or higher. In contrast, in Examples 1 to 11, where one high-refractive-index region is replaced with a polymeric monomer of a different structure, the haze % / total Δn is reduced to 3.5 or lower, resulting in a holographic recording medium with lower haze relative to the same total Δn.

[0587] In optical applications of AR glasses waveguides, a higher total Δn (light density) in 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 applications, cause waveguide light scattering, thus reducing light utilization efficiency and aesthetics. Therefore, by using the compound of this invention, which balances high total Δn and low haze, it is possible to produce AR glasses waveguides with excellent light utilization efficiency and aesthetics. Based on the above, the compounds of the present invention used in the embodiments are superior to the compounds of the comparative examples.

[0588] [Refractive Index] The refractive index of the polymerizable monomers produced in the Examples and Comparative Examples was determined using the following method. The results are shown in Table 2. The test solution was prepared by dissolving the sample in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate at a mass ratio of 4:1 to achieve a predetermined concentration. 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 indices as high refractive index monomers. As shown in Table 1, the holographic medium containing the compounds of the embodiments has the same or greater total Δn compared to the holographic medium containing the compounds of the comparative examples. Therefore, the compounds of the embodiments are superior to the compounds of the comparative examples in that they maintain the holographic recording performance while improving the compatibility with the medium.

[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 its entire contents are incorporated herein by reference.

Claims

1. A compound, characterized in that, It is represented by the following formula (1), In the formula, A represents a polymerizable group; the A is a (meth)acryloyl group; L represents a branched or unbranched (n+1) valence linker group; L is a chain-like aliphatic hydrocarbon group possessing an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. When n=1, L is selected from oxomylidene methylene group, oxomylidene ethoxy group, 1,3-oxomylidene propylidene group, 1,2-oxomylidene propylidene group, oxomylidene butylidene group, 2-hydroxyoxomylidene propylidene group, oxomylidene hexoxy group, oxomylidene heptoxy group, 3-oxomylidene pentoxy group, -OCH2CH2NHC(O)-, -OCH2CH2OCH2CH2NHC(O)-, -OCH 2CH2SCH2CH2-, -OCH2CH2NHC(S)-, -OCH2CH2OCH2CH2NHC(S)-, -OCH2CH2SCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, where in the case of n=2 or 3, L is selected from -(OCH2)2C(CH3)NHC(O)-, and any hydrogen atom in the chain aliphatic hydrocarbon group is replaced by a linking group formed by the substitution of any hydrogen atom with a bonding site to the polymerizable group A. R 1 It is a naphthalene ring, or... R 1 It is a fused aromatic heterocycle with or without substituents, or an aromatic hydrocarbon ring with an aromatic heterocycle as a substituent, wherein the fused aromatic heterocycle or the aromatic heterocycle is selected from benzothiazole ring, dibenzothiphene ring, or dithioxanthracene ring, and the aromatic hydrocarbon ring is a benzene ring. R 2 Represents a monovalent organogroup, with or without substituents; R 2 It has a ring structure, forming R 2 The number of rings is 1 to 3, and it has an aromatic hydrocarbon ring or an aromatic heterocycle as its ring structure; X 1 X 2 Each of the following can be used to independently represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents; m represents an integer of 0 or 1; n represents an integer from 1 to 3; p represents an integer of 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure; Where, R 1 =R 2 X 1 =X 2 Not all of the following are true simultaneously: p=1; The R 2 It has a partial structure selected from benzothiazole ring, benzene ring, thiadiazole ring, and dibenzothiophene ring.

2. The compound according to claim 1, wherein, The number of polymeric groups in formula (1) is 1.

3. The compound according to claim 1, wherein, The R 1 It is a fused aromatic ring group with or without substituents, or a monocyclic aromatic group substituted with an aromatic ring group.

4. The compound according to any one of claims 1 to 3, wherein, The R 2 It has a partial structure as shown in the following formula (2), In the formula, J represents a carbon atom with or without a substituent or a nitrogen atom with or without a substituent, and G represents a sulfur atom, an oxygen atom, or a nitrogen atom with or without a substituent.

5. A compound, characterized in that, It is represented by the following formula (3), In the formula, R 1 It is a naphthalene ring, or, R 1 It is a fused aromatic heterocycle with or without substituents, or an aromatic hydrocarbon ring with an aromatic heterocycle as a substituent, wherein the fused aromatic heterocycle or aromatic heterocycle is selected from benzothiazole rings, dibenzothiphene rings, and dithioxanthracene rings, and the aromatic hydrocarbon ring is a benzene ring; R 2 Represents a monovalent organogroup, with or without substituents; R 2 It has a ring structure, forming R 2 The number of rings is 1 to 3, and it has an aromatic hydrocarbon ring or an aromatic heterocycle as its ring structure; X 1 X 2 Each of the following can be used to independently represent an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents; p represents an integer 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure; Where, R 1 =R 2 X 1 =X 2 Not all of the following are true simultaneously: p=1; The R 2 It has a partial structure selected from benzothiazole ring, benzene ring, thiadiazole ring, and dibenzothiophene ring.

6. A method for manufacturing the compound according to claim 5, characterized in that, To induce a ring-opening reaction in the aliphatic cyclic compound represented by formula (4) below, In the formula, R 1 It is a naphthalene ring, or, R 1 It is a fused aromatic heterocycle with or without substituents, or an aromatic hydrocarbon ring with an aromatic heterocycle as a substituent, wherein the fused aromatic heterocycle or aromatic heterocycle is selected from benzothiazole rings, dibenzothiphene rings, and dithioxanthracene rings, and the aromatic hydrocarbon ring is a benzene ring; X 1 Represents an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents; p represents an integer of 1; Z represents an aliphatic linker with or without substituents and branched or unbranched; r represents an integer of 0 or 1. In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure.

7. The method for manufacturing the compound according to claim 6, wherein, The aliphatic cyclic compound represented by formula (4) is a compound represented by formula (5) or formula (6) below. In the formula, R 1 It is a naphthalene ring, or, R 1 It is a fused aromatic heterocycle with or without substituents, or an aromatic hydrocarbon ring with an aromatic heterocycle as a substituent, wherein the fused aromatic heterocycle or aromatic heterocycle is selected from benzothiazole rings, dibenzothiphene rings, and dithioxanthracene rings, and the aromatic hydrocarbon ring is a benzene ring; X 1 Represents an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents; p represents an integer 1; In the formula, there are 2 Rs 1 They can bond to each other at any position to form a ring structure.

8. A polymerizable composition comprising the compound of any one of claims 1 to 4 and a polymerization initiator.

9. A holographic recording medium comprising the polymeric composition of claim 8.

10. A polymer formed by polymerizing the polymeric composition of claim 8.

11. An optical material comprising the polymer of claim 10.

12. An optical component comprising the polymer of claim 10.

13. A high-capacity memory comprising the holographic recording medium of claim 9.

14. An optical element obtained for holographic recording in the holographic recording medium of claim 9.

15. An AR glasses comprising the optical element of claim 14.

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