Compounds, methods for producing the same, polymerizable compositions, polymers, holographic recording media, optical materials, and optical components

Abstract

A compound which is represented by formula (1). The present invention provides a compound which has high refractive index and excellent polymerizability, and which is useful as a starting material for an optical material, and the like. (In the formula, A represents a polymerizable group; L represents an optionally branched linking group having a valence of (n + 1); R1 represents an optionally substituted aromatic ring group; R2 represents an optionally substituted monovalent organic group; each of X1 and X2 independently represents an oxygen atom, a sulfur atom or an optionally substituted nitrogen atom; m represents an integer of 0 or 1; n represents an integer from 1 to 3; and p represents an integer of 0 or 1.　In the formula, two R1 moieties may combine with each other at arbitrary positions to form a ring structure.　Meanwhile, all of R1 = R2, X1 = X2 and p = 1 cannot be true at the same time in the formula.)

Description

[Technical Field]

[0001] This invention relates to a compound with a high refractive index, high transparency, and excellent polymerizability, and to a method for producing the same. Furthermore, this invention relates to a polymerizable composition containing the compound or a polymer thereof, as well as to a holographic recording medium, optical material, and optical component. [Background technology]

[0002] Traditionally, glass has been widely used as an optical material. For example, in the case of optical lenses, even for lenses with the same focal length, using a material with a high refractive index allows for thinner lenses, resulting in advantages such as reduced weight and increased design flexibility for the optical path. Furthermore, high refractive index optical lenses are effective in miniaturizing, increasing the resolution, and widening the angle of optical imaging devices.

[0003] In recent years, highly transparent plastics have attracted attention as an alternative optical material to glass. Compared to glass, plastic materials have advantages such as being easier to reduce in weight, easier to improve mechanical strength, and easier to process and mold. With the development of related technologies, the demand for improved performance in plastic optical materials is also increasing. For example, materials for optical lenses are required to be easily polymerizable, have good curability, and have a high refractive index of the polymer.

[0004] To date, many resins have been developed to increase the refractive index. For example, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is frequently used as a high refractive index acrylate. However, it has a relatively high viscosity, and the refractive index of the monomer is not sufficiently high, at around 1.62 (Patent Document 1). In addition to introducing aromatic rings, incorporating sulfur atoms into the molecule is also effective in increasing the refractive index. For example, Patent Document 2 describes a diacrylate monomer with a pentaerythritol skeleton having 1 to 2 naphthylthio groups in one molecule. In this case, the refractive index is 1.62 to 1.65. Patent document 3 describes an acrylate compound with a glycerol skeleton having two benzothiazole rings in one molecule. In this case as well, the refractive index is 1.63. These are not sufficient for applications requiring ultra-high refractive indices exceeding 1.65.

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

[0006] Patent document 6 relates to optical materials used in holographic recording media. Patent document 6 describes a pentaerythritol-type (meth)acrylate compound having three aromatic rings as an ultra-high refractive index compound. These compounds have a structure with three identical high-refractive index sites, which allows for a high refractive index. However, due to steric hindrance around the polymerizable group, sufficient polymerization performance may not be obtained, resulting in poor holographic recording characteristics.

[0007] [Patent Document 1] Japanese Patent Application Publication No. 6-220131 [Patent Document 2] Special Publication No. 2008-527413 [Patent Document 3] Japanese Patent 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 Publication No. 2017-14213 [Overview of the project]

[0008] The object of this invention is to provide a compound that is useful as an optical material or optical component, possessing high refractive index, high transparency, and easy polymerization.

[0009] The present inventors have found that a polymerizable pentaerythritol-type compound having different high-refractive-index moieties is a compound that combines the properties of high refractive index, high transparency, and high polymerizability, and that a polymerizable composition and a polymer obtained using the same have a high refractive index and high transparency.

[0010] That is, the gist of the present invention resides in the following.

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

[0012]

Chemical Formula

[0013] [In the formula, A represents a polymerizable group. L represents an optionally branched (n+1)-valent linking group. R 1 represents an optionally substituted aromatic ring group. R 2 represents an optionally substituted monovalent organic group. X 1 , X 2 each independently represent an oxygen atom, a sulfur atom, or an optionally substituted nitrogen atom. m represents an integer of 0 or 1. n represents an integer of 1 to 3. p represents an integer of 0 or 1. In the formula, two R 1 may be bonded to each other at any position to form a ring structure. Provided that in the formula, R 1 =R 2 , X 1 =X 2 and p=1 do not all hold true at the same time.] [2] The compound according to [1], wherein the number of polymerizable groups in the formula (1) is 1. [3] The compound according to [1] or [2], wherein A is an oxiranyl group, a vinyl group, an allyl group, or a (meth)acryloyl group. [4] The compound according to [3], wherein A is a (meth)acryloyl group. [5] The R 1The compound is one of the compounds described in any of [1] to [4], wherein the compound is a condensed aromatic ring group which may have substituents, or a monocyclic aromatic group which is substituted with an aromatic ring group. [6] The R 2 A compound according to any one of [1] to [5], having a substructure represented by the following formula (2).

[0014] [ka]

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

[0016] [ka]

[0017] [In the formula, R 1 R represents an aromatic ring group which may have substituents. 2 X represents a monovalent organic group which may have substituents. 1 , X 2 Each of these independently represents an oxygen atom, a sulfur atom, or an optionally substituted nitrogen atom. p represents an integer of 0 or 1. In the formula, two R 1 These elements may be joined to each other at arbitrary positions to form a ring structure. However, in the formula, R 1 =R 2 , X 1 =X 2 It is impossible for all of these conditions to hold simultaneously, such as p=1. [8] A method for producing the compound according to [7], characterized by performing a ring-opening reaction on an aliphatic cyclic compound represented by the following formula (4).

[0018] [ka]

[0019] [In the formula, R 1 X represents an aromatic ring group which may have substituents. 1 represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. p represents an integer of 0 or 1. Z represents an aliphatic linking group which may have substituents and may be branched. r represents an integer of 0 or 1. In the formula, two R 1 These elements may be joined to each other at any position to form a ring structure. [9] A method for producing the compound according to [8], wherein the aliphatic cyclic compound represented by formula (4) is a compound represented by the following formula (5) or formula (6).

[0020] [ka]

[0021] [In the formula, R 1 X represents an aromatic ring group which may have substituents. 1 represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. p represents an integer of 0 or 1. In the formula, two R 1 These elements may be joined to each other at any position to form a ring structure. A polymerizable composition containing a compound described in any of [1] to [6] and a polymerization initiator.

[11] Holographic recording medium comprising the polymerizable composition described in

[10] .

[12] A polymer obtained by polymerizing the polymerizable composition described in

[10] . Optical materials comprising the polymers described in

[13] and

[12] . Optical components comprising the polymers described in

[14] and

[12] .

[15]

[11] A large-capacity memory including a holographic recording medium. An optical element obtained by recording a hologram on the holographic recording medium described in

[16]

[11] . AR glasses including the optical elements described in

[17]

[16] . [Effects of the Invention]

[0022] The present invention provides a high refractive index compound that is useful as an optical material, possessing both high transparency and easy polymerization properties. The compounds of the present invention are particularly useful as reactive compounds for use in hard coat layers of optical lenses and optical components, and in holographic recording media. By using the compounds of the present invention, it is possible to realize optical materials and optical components with high diffraction efficiency, high light transmittance, and low turbidity. [Brief explanation of the drawing]

[0023] [Figure 1] Figure 1 is a schematic diagram showing the configuration of the device used for hologram recording. [Modes for carrying out the invention]

[0024] The embodiments of the present invention will be described in detail below. The present invention is not limited to the embodiments described below, and can be implemented with various modifications within the scope of its gist. In this invention, "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. In this invention, "may have substituents" means that it may have one or more substituents. "Nitrogen atom that may have substituents" also includes imino groups and the like when it does not have substituents.

[0025] 1. Regarding the compound of the present invention The compound of the present invention is represented by the following formula (1).

[0026] [ka]

[0027] [In the formula, A represents a polymerizable group. L represents a branched (n+1) valence linking group. R 1R represents an aromatic ring group which may have substituents. 2 X represents a monovalent organic group which may have substituents. 1 , X 2 Each of these independently represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. m represents an integer of 0 or 1. n represents an integer of 1 to 3. p represents an integer of 0 or 1. In the formula, two R 1 These elements may be joined to each other at arbitrary positions to form a ring structure. However, in the formula, R 1 =R 2 , X 1 =X 2 It is impossible for all of these conditions to hold simultaneously, such as p=1.

[0028] 1-1. Structure of the compound in formula (1) The compound of formula (1) has a pentaerythritol skeleton, and one of the four molecular chains bonded to this quaternary carbon atom has a polymerizable group. On the other hand, at least one of the remaining three molecular chains has a structure that exhibits a high refractive index. This allows for a higher refractive index of the polymer. Furthermore, in the compound represented by formula (1), two of these remaining three molecular chains have the same structure, and one has a different structure. This allows for a higher transparency of the polymer. A different structure is, in formula (1), -X 2 -R 2 It is a molecular chain represented by -(X 1 ) p -R 1 This means that it has a different structure from the molecular chain represented by R. 1 and R 2 , X 1 and X 2 Even if the constituent elements, substructures, and numbers are the same, if their bonding positions are different, -X 2 -R 2 ha-(X 1 ) p -R 1 It is considered to have a different structure from the other.

[0029] 1-2. Regarding A in equation (1) A is a polymerizable group, and its structure is not particularly limited. Examples of polymerizable groups include (meth)acryloyl group, allyl group, vinyl group, vinyl-substituted phenyl group, isopropenyl-substituted phenyl group, vinyl-substituted naphthyl group, isopropenyl-substituted naphthyl group, oxyranyl group, 2-methyloxyranyl group, oxetanyl group, etc., and a group suitable for the desired polymerization method can be selected. In photopolymerization using a photopolymerization initiator, oxyranyl group, vinyl group, allyl group, and (meth)acryloyl group are preferred. Of these, the (meth)acryloyl group is particularly preferred due to its high reactivity.

[0030] 1-3. Regarding L in equation (1) L represents a branched (n+1) valence linking group. L does not necessarily have to contain a complex atom, but from the viewpoint of ease of synthesis, it is preferable to have an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.

[0031] L is preferably an aliphatic hydrocarbon group having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, from the viewpoint of imparting high solubility to various media and avoiding discoloration in the compound of formula (1). The number of carbon atoms in the aliphatic hydrocarbon group (excluding the number of carbon atoms of substituents) is preferably 1 to 8. When the number of carbon atoms in the aliphatic hydrocarbon group is 8 or less, the refractive index of the compound of formula (1) does not decrease easily, the viscosity decreases due to the small molecular weight, and the processability tends to improve. The aliphatic hydrocarbon group constituting L may be either a cyclic aliphatic hydrocarbon group or a linear aliphatic hydrocarbon group, and these structures may be combined. A linear aliphatic hydrocarbon group is preferred from the viewpoint of mitigating steric hindrance around polymerizable group A.

[0032] Examples of linear aliphatic hydrocarbon groups having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent that constitutes L include, when n=1, oxomethylene group, oxoethylene group, 1,3-oxopropylene group, 1,2-oxopropylene group, oxobutylene group, 2-hydroxyoxopropylene group, oxohexylene group, oxoheptylene group, 3-oxopentylene group, -OCH2CH2NHC(O)-, -OCH2CH2OCH2CH2NHC(O)-, -OCH2CH2SCH2CH2-, -OCH2CH2NHC(S)-, -OCH2CH2OCH2CH2NHC(S)-, -OCH2CH2SCH2CH2NHC(S)-, -OCH2CH2NHC(S)-, etc. L may be a combination of two or more of these groups. Examples of L when n=2 or 3 include -(OCH2)2C(CH3)NHC(O)- and linking groups in which any hydrogen atom in the above-mentioned linear aliphatic hydrocarbon group is substituted with a bond to polymerizable group A. In this case, the polymerizable group may be bonded by a branched structure.

[0033] From the viewpoint of a high refractive index, L is preferably a cyclic group, and the rings included in the cyclic group constituting L may be monocyclic or fused ring structures. The number of rings included in L is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. Aromaticity is not necessarily required for the rings included in L, but in order to maintain a high refractive index while keeping the size of the rings in the overall molecule small, aromatic hydrocarbon rings are preferred. Examples of aromatic hydrocarbon rings constituting L include benzene rings, indene rings, naphthalene rings, azulene rings, fluorene rings, acenaphthylene rings, anthracene rings, phenanthrene rings, pyrene rings, and the like.

[0034] L may have substituents. Examples of substituents that L may have include halogen atoms (chlorine atoms, bromine atoms, iodine atoms), hydroxyl groups, mercapto groups, C1-C8 alkyl groups, C2-C8 alkenyl groups, C1-C8 alkoxy groups, phenyl groups, mesityl groups, tolyl groups, naphthyl groups, cyano groups, acetyloxy groups, C2-C9 alkylcarbonyloxy groups, C2-C9 alkoxycarbonyl groups, sulfamoyl groups, C2-C9 alkylsulfamoyl groups, C2-C9 alkylcarbonyl groups, phenethyl groups, hydroxyethyl groups, acetylamide groups, dialkylaminoethyl groups to which C1-C4 alkyl groups are attached, trifluoromethyl groups, C1-C8 alkylthio groups, C6-C10 aromatic ring thio groups, nitro groups, and the like.

[0035] 1-4. X in equation (1) 1 , X 2 About X 1 , X 2 Each of these independently represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. 1 , X 2 From the viewpoint of keeping the water absorption rate low, an oxygen atom or a sulfur atom is preferred, and a sulfur atom is more preferred to give a high refractive index. There are no particular restrictions on the group that may be substituted for the nitrogen atom, but preferred examples include alkyl groups having 1 to 8 carbon atoms such as methyl groups and ethyl groups, and aromatic hydrocarbon groups such as phenyl groups and naphthyl groups.

[0036] 1-5. R in equation (1) 1 About R 1 R represents an aromatic ring group which may have substituents. 1 The aromatic rings that make up a substance are broadly classified into aromatic hydrocarbon rings and aromatic heterocycles. Aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, biphenylene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings. Aromatic heterocycles include aromatic heterocycles containing one heteroatom such as 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.; aromatic heterocycles containing two or more heteroatoms such as imidazole rings, triazole rings, tetrazole rings, oxazole rings, thiazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, thiadiazole rings, etc.; benzoxazole rings, thienoxazole rings, thiazo Examples include rings formed by the fusion of two or three rings containing two or more heteroatoms, such as a loxazole ring, oxazoloxazole ring, oxazoloimidazole ring, oxazolopyridine ring, oxazolopyridazine ring, oxazolopyrimidine ring, oxazolopyrazine ring, naphthoxazole ring, quinolinoxazole ring, dioxazolopyrazine ring, phenoxazine ring, benzothiazole ring, phlothiazole ring, thienothiazole ring, thiazolothiazole ring, thiazoloimidazole ring, thienothiadhiazole ring, thiazolothiadhiazole ring, thiazolopyridine ring, thiazolopyridine ring, thiazolopyridine ring, thiazolopyrazine ring, naphthothiazole ring, quinolinothiazole ring, thianthrene ring, and phenothiazine ring.

[0037] R 1 From the viewpoint of ease of synthesis and availability, the aromatic hydrocarbon ring constituting the compound is preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, biphenylene ring, or fluorene ring. From the viewpoint of suppressing the fluorescence of the compound of formula (1), R 1 The aromatic hydrocarbon rings constituting the compound are more preferably benzene rings, naphthalene rings, biphenylene rings, and fluorene rings.

[0038] R 1As the aromatic heterocycle constituting the compound, a sulfur-containing aromatic heterocycle is preferred because it tends to increase the refractive index of the compound of formula (1). The sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the aromatic heterocycle. In addition to the sulfur atom, it may also have an oxygen atom, a nitrogen atom, or both an oxygen atom and a nitrogen atom as heteroatoms. From the viewpoint of avoiding discoloration and ensuring solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2. Examples of sulfur-containing aromatic heterocycles include aromatic heterocycles containing one sulfur atom, such as thiophene rings, benzothiophene rings, dibenzothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, thiopyran rings, naphthothiophene rings, dinaphthothiophene rings, and dibenzothiopyran rings; aromatic heterocycles containing two or more sulfur atoms, such as thiazole rings, isothiazole rings, benzothiazole rings, naphthothiazole rings, phenothiazine rings, thiazoloimidazole rings, thiazolopyridine rings, thiazolopyridine rings, dioxazolopyrazine rings, thiazolopyrazine rings, thiazoloxazole rings, dibenzobenzothiophene rings, thienoxazole rings, thienothiadazole rings, and thiazolothiadazole rings. The sulfur-containing aromatic heterocycle may be a monocycle or a fused ring. A fused ring is preferred from the viewpoint of achieving a high refractive index. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 in terms of facilitating the acquisition of raw materials and synthesis. In particular, in terms of high refractive index and low coloration, sulfur-containing aromatic heterocycles such as benzothiazole rings, dibenzothiophene rings, benzothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, and thianthrene rings are preferred.

[0039] R 1From the viewpoint of ease of synthesis, a nitrogen-containing aromatic heterocycle may be used as the aromatic heterocycle constituting the compound. The nitrogen-containing aromatic heterocycle has at least one nitrogen atom as a heteroatom constituting the aromatic heterocycle. In addition to the nitrogen atom, it may also have an oxygen atom, a sulfur atom, or both an oxygen atom and a sulfur atom as heteroatoms. From the viewpoint of avoiding discoloration, the number of heteroatoms constituting the nitrogen-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2. Nitrogen-containing aromatic heterocycles include aromatic heterocycles containing one nitrogen atom, such as pyrrole rings, indole rings, carbazole rings, benzocarbazole rings, dibenzocarbazole rings, pyridine rings, quinoline rings, isoquinoline rings, oxazole rings, thiazole rings, benzoxazole rings, naphthoxazole rings, benzothiazole rings, naphthothiazole rings, phenoxazine rings, phenothiazine rings, thienoxazole rings, thiazoloxazole rings, oxazoloxazole rings, phlothiazole rings, thienothiazole rings, and thiazolothiazole rings; imidazole rings, triazole rings, Examples include aromatic heterocycles containing two or more nitrogen atoms, such as tetrazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, thiadiazole rings, benzimidazole rings, oxazolomidazole rings, oxazolopyridine rings, oxazolopyridine rings, oxazolopyridine rings, quinolinoxazole rings, dioxazolopyrazine rings, thiazolomidazole rings, thiazolothiadiazole rings, thiazolopyridine rings, thiazolopyridine rings, thiazolopyrazine rings, and quinolinothiazole rings.

[0040] The nitrogen-containing aromatic heterocycle may be a monocycle or a fused ring. A fused ring is preferred from the viewpoint of achieving a high refractive index. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 in terms of facilitating the acquisition of raw materials and synthesis. In particular, in terms of high refractive index and low coloration, the nitrogen-containing aromatic heterocycles are preferably carbazole rings, benzocarbazole rings, dibenzocarbazole rings, pyridine rings, quinoline rings, isoquinoline rings, benzoxazole rings, benzothiazole rings, benzimidazole rings, and thiadiazole rings, and more preferably carbazole rings, benzocarbazole rings, dibenzocarbazole rings, benzoxazole rings, benzothiazole rings, benzimidazole rings, and thiadiazole rings.

[0041] R 1 The aromatic heterocycle constituting the compound may be an oxygen-containing aromatic heterocycle. This tends to improve the heat resistance and weather resistance of polymers made from the compound of formula (1) as a raw material. The oxygen-containing aromatic heterocycle has at least an oxygen atom as a heteroatom constituting the aromatic heterocycle. In addition to the oxygen atom, it may also have a nitrogen atom, a sulfur atom, or both a nitrogen atom and a sulfur atom as heteroatoms. From the viewpoint of ensuring heat resistance, the number of oxygen atoms constituting the oxygen-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2. Examples of oxygen-containing aromatic heterocycles include aromatic heterocycles containing one oxygen atom, such as furan rings, benzofuran rings, dibenzofuran rings, naphthofuran rings, benzonaphthofuran rings, dinaphthofuran rings, phenoxazine rings, oxazole rings, isoxazole rings, benzoxazole rings, benzoisoxazole rings, naphthoxazole rings, thienoxazole rings, thiazoloxazole rings, oxazolomidazole rings, and phlothiazole rings; and aromatic heterocycles containing two or more oxygen atoms, such as dibenzodioxin rings, oxazoloxazole rings, and dioxazolopyrazine rings.

[0042] The oxygen-containing aromatic heterocycle may be a monocycle or a fused ring. A fused ring is preferred from the viewpoint of achieving a high refractive index. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 in terms of facilitating the acquisition of raw materials and synthesis. In particular, in terms of high refractive index and low coloration, the oxygen-containing aromatic heterocycles are preferably dibenzofuran rings, benzonaphthofuran rings, dinaphthofuran rings, oxazole rings, isoxazole rings, benzoxazole rings, benzoisoxazole rings, and naphthoxazole rings, and more preferably dibenzofuran rings, benzonaphthofuran rings, dinaphthofuran rings, and benzoxazole rings.

[0043] These R 1 The aromatic ring constituting the compound may have substituents. Examples of substituents include halogen atoms such as chlorine, bromine, and iodine; C1-C8 alkyl groups; C2-C8 alkenyl groups; alkoxy groups; cyano groups; acetyloxy groups; C2-C9 alkylcarbonyloxy groups; C2-C9 alkoxycarbonyl groups; sulfamoyl groups; C2-C9 alkylsulfamoyl groups; C2-C9 alkylcarbonyl groups; phenethyl groups; hydroxyethyl groups; acetylamide groups; dialkylaminoethyl groups formed by bonding C1-C4 alkyl groups; trifluoromethyl groups; C1-C8 alkylthio groups; C6-C10 aromatic ring thio groups; and nitro groups. In particular, preferred groups include C1-C8 alkyl groups, C1-C8 alkoxyl groups, C1-C8 alkylthio groups, C6-C10 aromatic ring thio groups, cyano groups, acetyloxy groups, C2-C8 alkylcarboxyl groups, sulfamoyl groups, C2-C9 alkylsulfamoyl groups, and nitro groups.

[0044] These R 1 From the viewpoint of increasing the refractive index of the compound of formula (1), it is preferable that the aromatic ring constituting the compound has a group containing an aromatic ring as a substituent. The aromatic ring included in the substituent is R 1 This is synonymous with the aromatic ring that constitutes it. The aromatic rings included in these substituents are R 1 The substituent may be directly bonded to the aromatic ring at any position, or it may be bonded via an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, or it may be bonded via any linking group. Direct bonding of the substituent is more preferable.

[0045] Furthermore, by making the aromatic ring included in this substituent a sulfur-containing aromatic heterocycle, the refractive index of the compound of formula (1) tends to become higher. The definition of a sulfur-containing aromatic heterocycle is R 1 This is synonymous with [the above]. As the sulfur-containing aromatic heterocycle, a fused ring is more preferred, and in particular, a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, and a thianthrene ring are preferred.

[0046] R 1 There are no particular restrictions on the number of aromatic rings that the compound has as substituents, but from the viewpoint of ease of synthesis and solubility, 1 to 4 is preferred, and 1 to 2 is more preferred.

[0047] R 1 From the viewpoint of achieving both a high refractive index and high solubility in various media, the aromatic ring constituting the compound is preferably a condensed aromatic ring which may have substituents, or a monocyclic aromatic ring substituted with an aromatic ring group, and more preferably a condensed aromatic heterocycle which may have substituents, or an aromatic hydrocarbon ring having an aromatic heterocycle as a substituent.

[0048] R 1 The aromatic rings constituting the compound may consist of two or more selected from the aforementioned sulfur-containing aromatic heterocycles, nitrogen-containing aromatic heterocycles, and oxygen-containing aromatic heterocycles. For example, R 1 The aromatic ring constituting the compound may be a carbazole ring having a dibenzothiophene ring as a substituent. Compounds of formula (1) having such a structure tend to have a high refractive index.

[0049] R 1 The aromatic ring that makes up the equation is X in equation (1) when p=1. 1 It can be joined at any position. If p=0, R 1 The aromatic rings constituting the compound may be bonded to the pentaerythritol skeleton in formula (1) at any position.

[0050] In equation (1), the two R 1Preferably, when a higher refractive index is achieved while keeping the size occupied in the entire molecule small, they are bonded to each other at any arbitrary position to form a ring structure. On the other hand, when maintaining the flexibility of the entire molecule and achieving higher solubility in various media, the two R in formula (1) 1 are preferably not bonded to each other.

[0051] 1-6. R in formula (1) 2 Regarding R 2 represents a monovalent organic group. R 2 may be linear, branched or cyclic, and may be a combination of these structures according to the physical properties required for the compound of formula (1). R 2 is -X in formula (1) 2 -R 2 may be a structure selected from the above R as long as it is the above-described heterogeneous structure, and may have the same structure as R 1 may be a structure selected from the above R, and may be the same structure as R 1 [[ID=28 ]]

[0052] R 2 preferably has a ring structure from the viewpoint of increasing the refractive index of the compound of formula (1). This ring structure may be a monocyclic structure or a fused ring structure. From the viewpoint of high solubility of the compound of formula (1) in various media, R 2 the number of rings constituting is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2. R 2 aromaticity is not necessarily required for the rings constituting, but it is preferable to have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the ring structure because a high refractive index tends to be achieved while keeping the size occupied in the entire molecule small.

[0053] R 2 examples of the aromatic hydrocarbon ring constituting include a benzene ring, an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring. R 2The aromatic heterocycles that make up the rings include: furan rings, benzofuran rings, dibenzofuran rings, naphthofuran rings, benzonaphthofuran rings, dinaphthofuran rings, thiophene rings, benzothiophene rings, dibenzothiophene rings, naphthothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, pyrrole rings, indole rings, carbazole rings, pyridine rings, quinoline rings, isoquinoline rings, and other aromatic heterocycles containing one heteroatom; imidazole rings, triazole rings, tetrazole rings, oxazole rings, thiazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, thiadiazole rings, and other aromatic heterocycles containing two or more heteroatoms; benzoxazole rings, thienoxazole rings, thiazoloxazole rings, Examples include rings formed by the fusion of two or three rings containing two or more heteroatoms, such as oxazoloxazole rings, oxazoloimidazole rings, oxazolopyridine rings, oxazolopyridazine rings, oxazolopyridine rings, oxazolopyrazine rings, naphthoxazole rings, quinolinoxazole rings, dioxazolopyrazine rings, phenoxazine rings, benzothiazole rings, phlothiazole rings, thienothiazole rings, thiazolothiazole rings, thiazoloimidazole rings, thienothiadhiazole rings, thiazolothiadhiazole rings, thiazolopyridine rings, thiazolopyridine rings, thiazolopyridine rings, thiazolopyrazine rings, naphthothiazole rings, quinolinothiazole rings, thianthrene rings, and phenothiazine rings.

[0054] R 2 From the viewpoint of ease of synthesis of the compound of formula (1), it is preferable that it has a heterocyclic structure, and more preferably a structure that includes an azole ring which is 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, furazan rings, thiadiazole rings, tetrazole rings, etc. From the standpoint of efficiently obtaining the target product, R 2 It is even more preferable that it has a substructure represented by the following formula (2).

[0056]

Chem.

[0057] [In the formula, J represents an optionally substituted carbon atom or an optionally substituted nitrogen atom, and G represents a sulfur atom, an oxygen atom or an optionally substituted nitrogen atom.]]

[0058] The partial structure represented by formula (2) can be appropriately selected as needed. From the viewpoints of ease of synthesis of the compound of formula (1) and high solubility in various media, a thiazole ring, an oxazole ring, an imidazole ring, or a thiadiazole ring is particularly preferable.

[0059] As mentioned above, R 2 preferably has an aromatic heterocyclic ring from the viewpoint of increasing the refractive index of the compound of formula (1), and a fused aromatic heterocyclic ring is more preferred. R 2 Examples of the fused aromatic heterocyclic ring possessed include an indole ring, a benzothiazole ring, a benzoxazole ring, and a benzimidazole ring. A benzothiazole ring is particularly preferable because it tends to achieve both high refractive index and high solubility for the compound of formula (1).

[0060] The aforementioned R 2 ring structure may be directly bonded to X 2 at any position, or may be bonded to X via an optionally substituted aliphatic linking group 2It may be bonded to the aliphatic linking group. From the viewpoint of improving the solubility of the compound of formula (1) in various media, this aliphatic linking group is preferably in the form of a chain. By making this chain portion an aliphatic hydrocarbon group, the solubility tends to improve further. In this case, the number of carbon atoms (excluding the number of carbon atoms of substituents) is preferably 1 to 8. When the number of carbon atoms is 8 or less, the refractive index does not decrease easily, the viscosity tends to decrease due to the small molecular weight, and processability tends to improve. These aliphatic linking groups include methylene, ethylene, 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)-, and -C Examples include H2SC(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 have substituents. 2Examples of substituents that may be present include halogen atoms such as chlorine, bromine, and iodine, C1-C8 alkyl groups, C2-C8 alkenyl groups, C1-C14 aromatic hydrocarbon rings, aromatic heterocycles, alkoxyl groups, cyano groups, acetyloxy groups, C2-C9 alkylcarbonyloxy groups, C2-C9 alkoxycarbonyl groups, sulfamoyl groups, C2-C9 alkylsulfamoyl groups, C2-C9 alkylcarbonyl groups, phenethyl groups, hydroxyethyl groups, acetylamide groups, dialkylaminoethyl groups formed by bonding C1-C4 alkyl groups, trifluoromethyl groups, C1-C8 alkylthio groups, C6-C10 aromatic ring thio groups, and nitro groups. In particular, from the standpoint of availability, preferred members include C1-C8 alkyl groups, C1-C14 aromatic hydrocarbon rings, aromatic heterocycles, C1-C8 alkoxy groups, cyano groups, acetyloxy groups, C2-C8 alkylcarboxyl groups, sulfamoyl groups, C2-C9 alkylsulfamoyl groups, and nitro groups. Note, R 2 If the compound has a ring structure, from the viewpoint of increasing the refractive index of the compound of formula (1), groups containing aromatic rings may be appropriately selected and adopted as substituents. The aromatic rings included in the substituents are R 1 This is synonymous with the aromatic ring that constitutes it. The aromatic rings included in these substituents are R 2 The ring structure may be directly bonded at any position, or it may be bonded via an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, or it may be bonded via any linking group. The substituent is R 2 It is more preferable that the ring structure is directly bonded to the ring structure.

[0062] 1-7. Regarding m and n in equation (1) m represents an integer of 0 or 1. While m can be selected as appropriate, m=1 is preferred from the viewpoint of mitigating steric hindrance around polymerizable group A and increasing the reactivity of the compound of formula (1).

[0063] n represents an integer between 1 and 3. This value of n can be chosen as appropriate. For example, from the viewpoint of facilitating polymerization of the compound in formula (1), n ​​can be set to 2 or 3. On the other hand, since it tends to achieve a high refractive index, the compound of formula (1) preferably has fewer polymerizable groups, and more preferably is a monofunctional compound with 1 polymerizable group. That is, from the viewpoint of achieving a high refractive index, n=1 or 2 is preferred, and n=1 is more preferred.

[0064] 1-8.Molecular weight The compound of formula (1) preferably has a molecular weight of 2000 or less, more preferably 1500 or less, from the viewpoint of keeping viscosity low and maintaining good processability. The compound of formula (1) preferably has a molecular weight of 400 or more, more preferably 500 or more, and even more preferably 550 or more, from the viewpoint of reducing shrinkage rate during polymerization.

[0065] 1-9. Relationship between molecular structure and physical properties The compound of formula (1) can be used as a polymerizable compound (monomer) with a high refractive index by having a polymerizable group on one of the four molecular chains of the pentaerythritol skeleton, and having a structure that exhibits a high refractive index on at least one of the remaining three molecular chains. In particular, by appropriately introducing a high refractive index site with a heterogeneous structure as described above, it is possible to simultaneously ensure high solubility of the monomer in various media and adjust the compatibility between the polymer and the media after the polymerization reaction. For example, molecular chain-(X 1 ) p -R 1 This achieves a high refractive index. Molecular chain-X 2 -R 2 This ensures high compatibility with the target medium. As a result, a highly refractive and transparent polymer with low turbidity can be obtained.

[0066] 1-10. Exemplary Compounds Specific examples of compounds represented by formula (1) above are given below. The compounds of the present invention are not limited to these, unless they exceed the scope of the invention.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

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

[0074] [ka]

[0075] [In the formula, R 1 R represents an aromatic ring group which may have substituents. 2 X represents a monovalent organic group which may have substituents. 1 , X 2 Each of these independently represents an oxygen atom, a sulfur atom, or an optionally substituted nitrogen atom. p represents an integer of 0 or 1. In the formula, two R 1These elements may be joined to each other at arbitrary positions to form a ring structure. However, in the formula, R 1 =R 2 , X 1 =X 2 It is impossible for all of these conditions to hold simultaneously, such as p=1.

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

[0077] [ka]

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

[0079] The (meth)acrylate agent can be any compound having a (meth)acryloyl group or a group convertible to a (meth)acryloyl group, and capable of reacting with the active hydrogen of the hydroxyl group in formula (3). Examples of (meth)acrylate agents include (meth)acrylate salts, (meth)acrylic anhydride, (meth)acrylic acid esters, 3-chloropropionate salts, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

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

[0081] The basic compound may be one or more organic basic compounds (such as triethylamine, pyridine, and imidazole), one or more inorganic basic compounds (such as sodium carbonate and potassium carbonate), or a combination of one or more organic basic compounds and one or more inorganic basic compounds.

[0082] In the reaction between the compound of formula (3) and the (meth)acrylate agent, it is preferable to use an organic solvent. Examples of organic solvents include dimethoxyethane, dichloromethane, tetrahydrofuran (THF), toluene, and N,N-dimethylformamide (DMF). One organic solvent may be used, or two or more may be used in combination.

[0083] In the production of compound (1A), it is preferable to purify the reactant (crude) obtained from the synthesis reaction. Low coloration can be achieved by purifying and removing impurities. Known methods can be applied as purification methods. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods may be performed individually or in combination sequentially.

[0084] If compound (1A) is a solid at room temperature, it is preferable to use the recrystallization method because it allows for a high degree of removal of coloring substances.

[0085] Examples of recrystallization solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, t-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; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, 2-methoxyethanol, 2-butoxyethanol, and propylene glycol monomethyl ether; glycols such as ethylene glycol and diethylene glycol; and water. These solvents may be used individually or in combination of two or more.

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

[0087] For example, although yields may be low and isolation and purification may be burdensome, the compound of formula (3) can be synthesized by simultaneously or sequentially linking the following compounds (c-1) and (c-2), which have high refractive index sites, by a nucleophilic substitution reaction with pentaerythritol trihalide (b).

[0088] [ka]

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

[0090] [ka]

[0091] [In the formula, R 1 X represents an aromatic ring group which may have substituents. 1 represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. p represents an integer of 0 or 1. Z represents an aliphatic linking group which may have substituents and may be branched. r represents an integer of 0 or 1. In the formula, two R 1 These elements may be joined to each other at any position to form a ring structure.

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

[0093] When r=1, Z represents an aliphatic linking group that may have substituents and may be branched. Examples of aliphatic cyclic compounds of formula (4) include cyclic carbonate compounds, cyclic carbamate compounds, cyclic thiocarbonate compounds, cyclic thiocarbamate compounds, cyclic sulfate ester compounds, cyclic sulfite ester compounds, and cyclic phosphate ester compounds.

[0094] In the preparation of the compound of formula (3), the aliphatic cyclic compound of formula (4) can be appropriately selected and prepared as needed. For the aliphatic cyclic compound of formula (4), it is preferable to use an oxetane compound represented by the following formula (5) or a cyclic carbonate compound represented by the following formula (6), as these offer the advantage of obtaining compounds that exhibit both high refractive index and high solubility.

[0095] [ka]

[0096] [In the formula, R 1 X represents an aromatic ring group which may have substituents. 1 represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. p represents an integer of 0 or 1. In the formula, two R 1may be bonded to each other at any position to form a ring structure.]

[0097] <Example of synthesis of aliphatic cyclic compound of formula (4) where r=1> As shown in the following reaction formula, intermediate (e) is obtained by reacting pentaerythritol trihalide (b) with any one reagent (d) selected from the group consisting of a cyclic carbonation reagent, a cyclic carbamation reagent, a cyclic thiocarbonation reagent, a cyclic thiocarbamation reagent, a cyclic sulfation reagent, a cyclic sulfitation reagent and a cyclic phosphation reagent. Further, the aliphatic cyclic compound of formula (4) can be synthesized by linking a compound (c-1) having a high-refractive-index site to the intermediate (e).

[0098] The aliphatic cyclic compound of formula (4) can also be synthesized by causing compound (f) to act on intermediate (e) to introduce a partial structure of the high-refractive-index site in advance, and then bonding the obtained intermediate (g) with compound (h).

[0099] Instead of pentaerythritol trihalide (b), the aliphatic cyclic compound of formula (4) can be synthesized by linking a compound (c-1) having a high-refractive-index site to pentaerythritol dihalide (i) to obtain an intermediate (j), and then reacting the intermediate (j) with reagent (d).

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

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

[0102]

Chemical Formula

[0103] <Example of synthesis of aliphatic cyclic compound of formula (4) where r=0> In this case, the aliphatic cyclic compound of formula (4) is the oxetane compound represented by formula (5). As shown in the reaction equation below, 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 to obtain an intermediate (k), and then linking it with a compound (c-1) having a high refractive index.

[0104] The compound of formula (5) can also be synthesized by reacting intermediate (k) with compound (f) to pre-introduce a substructure of the highly refractive region, and then bonding the resulting intermediate (l) with compound (h).

[0105] By reacting the compound of formula (5) with compound (c-2) having a high refractive index site, the high refractive index site can be introduced while opening the oxetane structure, and the compound of formula (3) can be synthesized.

[0106] [ka]

[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 polymerization initiator causes the polymerizable functional group A of the compound of formula (1) to undergo a polymerization reaction, thereby obtaining the polymer of the present invention.

[0108] 2-1. Polymerization Initiators The type of polymerization initiator is not particularly limited; it can be appropriately selected from known polymerization initiators depending on the polymerization method. Similarly, the polymerization method is not limited; 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 composition of the present invention include radical polymerization initiators, redox polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. In addition, photocationic polymerization initiators that generate active species cations upon light irradiation can also be used. The examples of polymerization initiators described later include those generally referred to as polymerization catalysts.

[0110] 2-1-1. Radical polymerization initiators <Photopolymerization initiator> Any known photoradical polymerization initiator can be used to assist in the polymerization of the polymerizable composition of the present invention. Examples include azo compounds, azide compounds, organic peroxides, organic borates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, oxime esters, etc. Among these, benzophenones, acylphosphine oxide compounds, oxime ester compounds, etc. are preferred as photopolymerization initiators from the viewpoint of compatibility and availability.

[0111] Specific examples of photopolymerization initiators include benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-mol Examples include pholinophenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine 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-methylpropan-1-one and methylbenzoyl formate, 1-[4-(phenylthio)-2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)ethanone, etc.

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

[0113] The amount of photopolymerization initiator in the polymerizable composition of the present invention is usually 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, when the total amount of all radically polymerizable compounds in the polymerizable composition is 100 parts by mass. The upper limit is usually 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, polymerization will proceed rapidly, which may not only increase the birefringence of the cured product but also worsen its hue. On the other hand, if too little is added, the polymerizable composition may not polymerize sufficiently.

[0114] <Thermal polymerization initiator> Any known thermal radical polymerization initiator can be used as a thermal polymerization initiator to assist in the polymerization of the polymerizable composition of the present invention. 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 in the polymerization reaction.

[0115] Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dicumyl peroxide and di-t-butyl peroxide. Examples include dialkyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; and peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 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-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitride, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane)dihydrochloride.

[0117] These thermal polymerization initiators may be used individually or in combination of two or more in any combination and ratio.

[0118] The content of the thermal polymerization initiator in the polymerizable composition of the present invention is usually 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, when the total amount of all radically polymerizable compounds in the polymerizable composition is 100 parts by mass. The upper limit is usually 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, polymerization will proceed too rapidly, which may impair the optical uniformity of the resulting polymer and worsen its hue. On the other hand, if there is too little, thermal polymerization may not proceed sufficiently.

[0119] When using both a photopolymerization initiator and a thermal polymerization initiator, their mass ratio is usually 100:1 to 1:100 (photopolymerization initiator: thermal polymerization initiator, the same applies hereafter in this paragraph), preferably 10:1 to 1:10. Too little thermal polymerization initiator may result in insufficient polymerization, while too much may cause discoloration.

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

[0121] Specific examples of redox polymerization initiators include combination systems of dibenzoyl peroxide as a peroxide with aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as reducing agents; combination systems of hydroperoxide as a peroxide with metal soaps as reducing agents; and combination systems of hydroperoxide as a peroxide with thioureas as reducing agents. In water-soluble redox polymerization initiators, peroxides such as persulfates, hydrogen peroxide, and hydroperoxides are converted into water-soluble inorganic reducing agents (Fe 2+ It is used in combination with organic reducing agents (such as NaHSO3) or organic reducing agents (such as alcohols and polyamines).

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

[0123] 2-1-3. Anionic polymerization initiators Examples of anionic polymerization initiators used in the polymerizable composition of the present invention include alkali metals, n-butyllithium, sodium amide, sodium naphthalenide, Grignard reagents, lithium alkoxide, and alkali metal benzophenone ketyl. These may be used individually or in any combination and ratio of two or more.

[0124] 2-1-4. Cationic polymerization initiators Examples of cationic polymerization initiators used in the polymerizable composition 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 chlorotriphenylmethane. Any one of these may be used alone, or two or more may be used in any combination and ratio.

[0125] The amount of anionic polymerization initiator or cationic polymerization agent in the polymerizable composition of the present invention is usually 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, per 100 parts by mass of the total amount of all anionic or cationic polymerizable compounds in the polymerizable composition. The upper limit is usually 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 amount of anionic or cationic polymerization initiator is less than 0.001 parts by mass, a sufficient reaction will not occur, and if it exceeds 5 parts by mass, it becomes difficult to balance the pot life and polymerization rate.

[0126] 2-1-5. Photocationic polymerization initiators In this invention, a photocationic polymerization initiator is an initiator that generates cation species upon light. While the photocationic polymerization initiator is not particularly limited as long as it is a compound that generates cation species upon light irradiation, onium salts are generally well known. Examples of onium salts include diazonium salts of Lewis acids, iodnium salts of Lewis acids, and sulfonium salts of Lewis acids. Specifically, examples include phenyldiazonium salt of boron tetrafluoride, diphenyliodnium salt of phosphorus hexafluoride, diphenyliodnium 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 bishexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, and diphenyl-4-phenylthiophenylsulfonium hexafluoroantimonate. Examples include UVI-6992 from Dow Chemical, CPI-100P from Sunapro, CPI-101A from Sunapro, CPI-200K from Sunapro, and Omnicat 270 from IGM Resins.

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

[0129] The amount of photocationic polymerization initiator in the polymerizable composition of the present invention is preferably 0.02 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, based on 100 parts by mass of the total of all photocationically polymerizable compounds in the polymerizable composition. If the amount of photocationic polymerization initiator is less than 0.02 parts by mass, a sufficient reaction will not occur, and if it exceeds 20 parts by mass, it becomes difficult to balance both pot life and polymerization rate.

[0130] When using a photocationic polymerization initiator, the aforementioned cationic polymerization initiator may be used in combination. In that case, the cationic polymerization initiator is usually used in an amount of 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the cationic polymerizable compound in the polymerizable composition. If the amount of cationic polymerization initiator used is too small, the polymerization rate will be slow, while if it is too large, the physical properties of the resulting polymer may deteriorate.

[0131] Furthermore, when using photocationic polymerization initiators, photocationic polymerization sensitizers can also be used in combination. Photocationic polymerization sensitizers are formulations that efficiently transfer the energy of the irradiation light to the photocationic polymerization initiator when the irradiation light of the light source used for photocationic polymerization and the absorption wavelength of the photocationic polymerization initiator do not match well. Known examples include phenolic compounds such as methoxyphenol (Japanese Patent Publication No. 5-230189), thioxanthone compounds (Japanese Patent Publication No. 2000-204284), and dialkoxyanthracene compounds (Japanese Patent Publication No. 2000-119306).

[0132] The photocationic polymerization sensitizer is typically used in an amount of 0.2 to 5 parts by mass, preferably 0.5 to 1 part by mass, per 1 part by mass of the photocationic polymerization initiator. If the amount of photocationic polymerization sensitizer is too small, the sensitizing effect may not be easily achieved, while if it is too large, the physical properties of the polymer may deteriorate.

[0133] 2-2. About polymerizable compounds The polymerizable composition of the present invention may contain any one of the compounds of the present invention represented by formula (1) alone, or it may contain two or more in any combination and ratio.

[0134] The polymerizable composition of the present invention may contain other polymerizable compounds besides the compound of the present invention.

[0135] The content of the compound of the present invention in the polymerizable composition of the present invention is preferably 1% by mass or more and 99% by mass or less, and more preferably 5% by mass or more and 95% by mass or less, in terms of the ratio to the total solid content of the polymerizable composition of the present invention. If the content of the compound of the present invention is less than 1% by mass, the effect of using the compound of the present invention will not be fully exhibited, while if it exceeds 99% by mass, the curability tends to decrease.

[0136] Other examples of polymerizable compounds include cationic polymerizable monomers, anionic polymerizable monomers, and radical polymerizable monomers. These polymerizable compounds may be used individually or in any combination and ratio of two or more. Polymerizable compounds having two or more polymerizable functional groups in a single molecule (sometimes called polyfunctional monomers) can also be used. When polyfunctional monomers are used, cross-linked structures are formed within the polymer, which can improve thermal stability, weather resistance, and solvent resistance.

[0137] If the polymerizable composition of the present invention contains other polymerizable compounds other than the compound of the present invention, the content thereof is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 5% by mass or less, in terms of the ratio to the total solid content of the polymerizable composition of the present invention. If the content of other polymerizable compounds is less than 0.1% by mass, the effect of imparting properties by their addition is not fully exhibited, while if it exceeds 5% by mass, problems such as impaired optical properties and strength tend to occur.

[0138] <Cationic polymerizable monomers> Examples of cationic polymerizable monomers include compounds having an oxirane ring, styrene and its derivatives, vinylnaphthalene and its derivatives, vinyl ethers, N-vinyl compounds, and compounds having an oxetane ring. In particular, it is preferable to use a compound having at least an oxetane ring, and even more preferably to use a compound having an oxirane ring in combination with a compound having an oxetane ring.

[0139] Examples of compounds containing an oxirane ring include prepolymers that contain two or more oxirane rings within a single molecule. Examples of such prepolymers include alicyclic polyepoxys, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, 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, and divinylbenzene.

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

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

[0143] Examples of N-vinyl compounds include N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, and N-vinylphenothiazine.

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

[0145] These cationic polymerizable monomers may be used individually or in any combination and 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 methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc.); acrylic acid esters (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 malonic acid ester, cyanoacrylate ester, vinylidene cyanide, etc.).

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

[0150] <Radical polymerizable monomers> Radical polymerizable monomers are compounds that have one or more ethylenically unsaturated double bonds in a single molecule. Examples include (meth)acrylic acid esters, (meth)acrylamides, vinyl esters, and styrenes.

[0151] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, (n- or i-)propyl (meth)acrylate, (n-, i-, sec- or t-)butyl (meth)acrylate, amyl (meth)acrylate, adamantyl (meth)acrylate, chloroethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, benzyl (meth)acrylate, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, and hydroxybenzyl Zyl (meth)acrylate, hydroxyphenethyl (meth)acrylate, dihydroxyphenethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenyl (meth)acrylate, hydroxyphenyl (meth)acrylate, chlorophenyl (meth)acrylate, sulfamoylphenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-(hydroxyphenylcarbonyloxy)ethyl (meth)acrylate, phenol EO modified (meth)acrylate, phenylphenol EO modified (meth)acrylate, paracumylphenol EO modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, bisphenol F EO modified diacrylate, bisphenol AExamples include EO-modified diacrylate, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenoxyethanol ful orange (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Here, "EO" means "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-(hydroxyphenyl)(meth)acrylamide, N-(sulfamoylphenyl)(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, and the like.

[0153] Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, t-butyl vinyl benzoate, vinyl chlorobenzoate, vinyl 4-ethoxybenzoate, vinyl 4-ethyl vinyl benzoate, vinyl 4-methyl vinyl benzoate, vinyl 3-methyl vinyl benzoate, vinyl 2-methyl vinyl benzoate, vinyl 4-phenyl vinyl benzoate, and vinyl pivalate.

[0154] Examples of styrenes 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, and divinylbenzene.

[0155] These radical polymerizable monomers may be used individually or in any combination and ratio of two or more.

[0156] Any of the cationic polymerizable monomers, anionic polymerizable monomers, and radical polymerizable monomers exemplified above can be used, or two or more may be used in combination. For holographic recording media, it is preferable to use radical polymerizable monomers as other polymerizable compounds used in combination with the compound of the present invention represented by formula (1), for the reason that they do not easily inhibit the reaction that forms the resin matrix.

[0157] 2-3 Other Additives Other components may be added to the polymerizable composition of the present invention, as long as they do not impair the effects of the present invention.

[0158] Other components include, for example, solvents, antioxidants, plasticizers, ultraviolet absorbers, sensitizers, chain transfer agents, defoaming agents, polymerization inhibitors, and various additives such as fillers, diffusers, pigments, phosphors, and other wavelength conversion materials consisting of organic or inorganic substances.

[0159] The polymerizable composition of the present invention may contain a solvent for viscosity adjustment.

[0160] Specific examples of the solvent include, depending on the physical properties of the polymerizable composition, for example: alcohols such as ethanol, propanol, isopropanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as hexane, pentane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride 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; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; 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; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; nitriles such as acetonitrile and benzonitrile; and organic solvents such as N-methylpyrrolidone.

[0161] These solvents may be used alone or as a mixed solvent. Further, depending on the polymerization method (such as emulsion polymerization or suspension polymerization), water may also be used. When a solvent (or dispersion medium) is used, the amount thereof is not particularly limited, and may be adjusted and used to obtain a polymerizable composition having a suitable viscosity according to the polymerization method, processing method, and application.

[0162] In the present invention, in order to improve the heat-resistant yellowing resistance and weather resistance of the obtained polymer, it is preferable to incorporate an antioxidant or a light stabilizer as an additive into the polymerizable composition.

[0163] Specific examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, n-octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; and phosphorus-based antioxidants such as triphenyl phosphite, trisisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, tris(nonylphenyl)phosphite, tristridecyl phosphite, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexan-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocine, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and tris(2,4-di-t-butylphenyl)phosphite. These may be used alone or in combination of two or more kinds.

[0164] As the antioxidant, it is preferable to use a phenolic antioxidant and a phosphorus-based antioxidant in combination. Preferable combinations of the phenolic antioxidant and the phosphorus-based antioxidant include a combination of at least one selected from the group consisting of tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane and n-octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate as the phenolic antioxidant, and tris(2,4-di-t-butylphenyl)phosphite as the phosphorus-based antioxidant.

[0165] The amount of antioxidant in the polymerizable composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total amount of polymerizable composition, in terms of ensuring good heat resistance to yellowing of the resulting polymer.

[0166] Hindered amine light stabilizers (HALS) are preferably used as light stabilizers. Specific examples of HALS include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidine-4-yl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and Adekastab L. Examples include A-68 (manufactured by ADEKA Corporation), Adeka Stab LA-63P (manufactured by ADEKA Corporation), butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), tinuvin 111FDL, tinuvin 123, tinuvin 144, tinuvin 152, tinuvin 249, tinuvin 292, and tinuvin 5100 (all manufactured by BASF). These can be used individually or in combination of two or more.

[0167] The amount of light stabilizer in the polymerizable composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total amount of polymerizable composition, in terms of improving the heat resistance, yellowing, and weather resistance of the resulting polymer.

[0168] Antioxidants and light stabilizers can be used individually or in combination of two or more types.

[0169] 2-4 Method for producing polymerizable compositions The polymerizable composition of the present invention may be manufactured by mixing each component, or by pre-mixing the components other than the polymerization initiator and adding the polymerization initiator immediately before the polymerization reaction.

[0170] 3. Polymerization method of the polymerizable composition of the present invention The polymerization method for the polymerizable composition of the present invention is not particularly limited, but may include a method of polymerization by irradiation with active energy rays or a method of polymerization by heating.

[0171] 3-1. Polymerization Initiation Method (Activated Energy Rays) When photoradical polymerization of the polymerizable composition of the present invention is carried out by irradiation with active energy rays. The preferred active energy beams are electron beams or light in the ultraviolet to infrared wavelength range. As light sources, for example, if the active energy beam is ultraviolet, a 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. Other light sources such as lasers and LEDs can also be used.

[0172] The irradiation dose of the active energy rays is set appropriately according to the type of light source, the thickness of the coating film, etc. Preferably, it is set appropriately so that the reaction rate of the total amount of polymerizable functional groups of the compound of the present invention represented by formula (1) and other polymerized compounds is 80% or more, more preferably 90% or more. The reaction rate is calculated from the change in the absorption peak intensity of the polymerizable functional groups before and after the reaction using infrared absorption spectroscopy. After polymerization is initiated by irradiation with active energy rays, further polymerization may be carried out by heat treatment or annealing treatment as needed. The heating temperature is preferably in the range of 80 to 200°C. The heating time is preferably in the range of 10 to 60 minutes.

[0173] 3-2. Polymerization initiation method (heating) When heat-treating the polymerizable composition of the present invention for polymerization, 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 lower than 80°C, the heating time needs to be longer, which tends to be economically uneconomical. If the heating temperature is higher than 200°C, the energy cost is high, and the heating and cooling times are also long, which also tends to be economically uneconomical.

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

[0175] 4-1. Refractive Index Generally, polymerization increases the overall density, so the refractive index of the polymer tends to be higher than that of its precursor compound (called a monomer). By using monomers with high refractive indices and allowing the polymerization reaction to proceed sufficiently, the refractive index of the resulting polymer can be increased. Therefore, it is considered important to improve the refractive index of the polymer through the molecular structure design of the monomers. While refractive index is generally higher when evaluated with short-wavelength illumination, samples exhibiting a relatively high refractive index at short wavelengths will also exhibit a relatively high refractive index at long wavelengths, and this relationship does not reverse. Therefore, by evaluating and comparing refractive indices at a constant wavelength, it is possible to compare the inherent magnitude of the refractive index of the material. In this invention, the value at an illumination wavelength of 587 nm was used as the reference.

[0176] The refractive index of the polymer of the present invention is preferably 1.55 or higher, more preferably 1.60 or higher, particularly 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, but it is usually 2.0 or lower. When the polymer of the present invention is used as an optical material such as a lens, if the refractive index is less than 1.55, the central part of the optical lens may become thicker, which is undesirable as it impairs the lightweight properties that are characteristic of plastics. Furthermore, in the development of precision optical components such as lenses, it is important to achieve optical properties suitable for the component by combining optical materials with multiple refractive indices. From this viewpoint, polymers with a refractive index exceeding 1.63 can be said to be particularly useful materials for optical components.

[0177] When the polymer of the present invention is used as a recording layer material for a holographic recording medium, the refractive index of the polymer of the present invention is usually in the range of 1.65 or more and 1.78 or less, preferably 1.77 or less. If the refractive index is less than 1.65, the diffraction efficiency is low and the multiplicity is insufficient. If the refractive index is greater than 1.78, the difference in refractive index with the matrix resin becomes too large, causing increased scattering and a decrease in transmittance, requiring more energy for recording and playback.

[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, particularly preferably 120°C or higher, and also preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. If the temperature falls below this range, the optical properties may change from the design values ​​under the usage environment, and the practically required heat resistance may not be met. If the temperature exceeds this range, the processability of the polymer may decrease, making it difficult to obtain molded articles with a good appearance and high dimensional accuracy. In addition, the polymer may become brittle, reducing its mechanical strength and worsening the handling of the molded articles.

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

[0180] Examples of optical materials include optical overcoats, hard coat agents, adhesives for optical members, resins for optical fibers, and acrylic resin modifiers. Examples of optical components include lenses, filters, diffraction gratings, prisms, light guides, cover glasses for display devices, photosensors, photoswitches, LEDs, light-emitting elements, optical waveguides, optical splitters, optical fiber adhesives, substrates for display elements, substrates for color filters, substrates for touch panels, polarizing plates, display backlights, light guide plates, antireflection films, viewing angle expansion films, optical recording, stereolithography, and photorelief printing. The polymer of the present invention can also be used as layers of these optical components. Examples thereof include display protective films.

[0181] Among these applications, the polymer of the present invention can be particularly preferably applied to plastic lenses due to its high refractive index characteristics. Examples of the lenses include imaging lenses for cameras (in-vehicle cameras, digital cameras, cameras for PCs, cameras for mobile phones, surveillance cameras, etc.), spectacle lenses, light beam condensing lenses, and light diffusing lenses. For lenses produced using the polymer of the present invention, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, and dyeing treatment can be performed as needed to improve properties including antireflection performance, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting anti-fogging properties, or imparting fashionability.

[0182] 6. Hologram Recording Medium The polymerizable composition of the present invention can be suitably used for a recording layer of a hologram recording medium. In this case, the polymerizable composition of the present invention is preferably a photoreactive composition comprising, in addition to the compound of the present invention, a matrix resin, a photopolymerization initiator, a radical scavenger, and other additives. Details when used as a material for a hologram recording medium are described below.

[0183] 6-1. 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 substance that does not undergo significant chemical or physical changes upon irradiation with light, and is mainly composed of polymers of organic compounds.

[0184] Since the matrix resin, together with the polymerizable compounds and photopolymerization initiators described later, constitutes the polymerizable composition of the present invention, it is strongly required to have excellent compatibility with the polymerizable compounds and photopolymerization initiators. If the matrix resin has low compatibility with the other components, it will create an interface between the materials, and light will be refracted or reflected at the interface, causing light to leak into unwanted areas. This can lead to distortion or breakage of interference fringes, resulting in recording in inappropriate areas and potentially causing degradation of information. The compatibility between the matrix resin and the other components can be evaluated, for example, based on the scattered light intensity obtained by setting up a detector in a direction different from the transmitted light relative to the sample, as described in Japanese Patent Publication No. 3737306.

[0185] The matrix resin of the polymerizable composition of the present invention may consist of multiple materials soluble in a solvent within the polymerizable composition, and a resin may be used in which these materials are three-dimensionally crosslinked after being formed into a usable state. Examples include thermoplastic resins, thermosetting resins, and photocurable resins, as described below.

[0186] The three-dimensionally crosslinked resin is solvent-insoluble and is a reaction-cured product of a polymerizable compound that is liquid at room temperature and a compound that is reactive with the polymerizable compound. The three-dimensionally crosslinked resin acts as a physical obstacle, suppressing volume changes during recording. That is, in the recording layer after recording, bright areas tend to expand and dark areas tend to contract, resulting in unevenness on the surface of the holographic recording medium. To suppress this volume change, it is more preferable to use a polymerizable composition containing a three-dimensionally crosslinked resin matrix in the recording layer. In this context, a thermosetting resin is preferred as the matrix resin from the viewpoint of adhesion to the support. The resin materials that can be used as the matrix resin are described in detail below.

[0187] 6-1-1.Thermoplastic resin Specific examples of thermoplastic resins include chlorinated polyethylene, polymethyl methacrylate (PMMA), copolymers of methyl methacrylate and other alkyl acrylates, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate (PVAC), polyvinyl alcohol, polyvinyl formal, polyvinylpyrrolidone, cellulose resins such as ethyl cellulose and nitrocellulose, polystyrene resins, and polycarbonate resins. These can be used individually or in combination of two or more.

[0188] There are no particular restrictions on the solvents used for these thermoplastic resins, as long as they can dissolve them. 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. These can be used individually or in combination of two or more.

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

[0190] The former is convenient because it reacts immediately upon mixing, but when molding is involved, such as with holographic recording media, there is little time to adjust the process. On the other hand, the latter allows for free selection of curing temperature and time by appropriately choosing the type and amount of catalyst used, making it suitable for curing while molding, such as with holographic recording media. Since various types of resin raw materials, from low molecular weight to high molecular weight, are commercially available, they can be selected while maintaining compatibility with polymerizable reactive compounds and photoinitiators, as well as adhesion to the substrate. The following describes each ingredient, but each ingredient may be used individually or in combination of two or more.

[0191] <Epoxy> Examples of epoxy include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerin; alicyclic epoxy compounds having 4- to 7-membered ring cyclic aliphatic groups such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; bisphenol A type epoxy compounds; hydrogenated bisphenol A type epoxy compounds; bisphenol F type epoxy compounds; and phenol or cresol novolac type epoxy compounds.

[0192] Epoxys are preferably those having two or more epoxy groups in one molecule, but the type is not particularly limited. If the number of epoxy groups is too small, the required hardness as a matrix may not be achieved. There is no particular upper limit to the number of epoxy groups in one molecule, but it is usually 8 or less, and preferably 4 or less. If the number of epoxy groups is too large, it may take a long time to consume the epoxy groups, and the formation of the matrix resin may take too long.

[0193] <amine> As the amine, one containing a primary amino group or a secondary amino group can be used. Examples of such amines include aliphatic polyamines such as ethylenediamine, diethylenetriamine and its derivatives; alicyclic polyamines such as isophoronediamine, menthanediamine, N-aminoethylpiperazine and its derivatives; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and its derivatives; polyamides such as condensates of dicarboxylic acids such as dimer acid and the above-mentioned polyamines; imidazole compounds such as 2-methylimidazole and its derivatives; and other examples such as dicyandiamide and adipic acid dihydrazide.

[0194] <Thiol> Examples of thiols include dithiols such as 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, and 1,9-nonanedithiol, as well as thiol compounds such as thiocol (manufactured by Toray Fine Chemicals) and jER Cure QX40 (manufactured by Mitsubishi Chemical Corporation). Among these, commercially available fast-curing polythiols such as jER Cure QX40 are preferably used.

[0195] <phenol> Examples of phenols include bisphenol A, novolac-type phenolic resins, and resol-type phenolic resins.

[0196] <Acid anhydride> Examples of acid anhydrides include monofunctional acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride and its derivatives, and bifunctional acid anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic anhydride and its derivatives.

[0197] <Amount of amines, thiols, phenols, and acid anhydrides used> The amount of amines, thiols, phenols, and acid anhydrides used, expressed as a percentage of the moles of epoxy groups, is usually 0.1 equivalents or more, preferably 0.7 equivalents or more, and usually 2.0 equivalents or less, preferably 1.5 equivalents or less. If the amount of amines, thiols, phenols, and acid anhydrides used is too little or too much, there will be a large number of unreacted functional groups, which may impair storage stability.

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

[0199] Anionic polymerization initiators generate anions by heat or irradiation with active energy rays, and examples include amines. Examples of amines include amino group-containing compounds such as dimethylbenzylamine, dimethylaminomethylphenol, and 1,8-diazabicyclo[5.4.0]undecene-7, and their derivatives; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole, and their derivatives. These can be used individually or in combination depending on the curing temperature and curing time.

[0200] Cationic polymerization initiators generate cations by heat or irradiation with active energy rays, and examples include aromatic onium salts. Specific examples include compounds consisting of anionic components such as SbF6-, BF4-, AsF6-, PF6-, CF3SO3-, and B(C6F5)4-, and aromatic cationic components containing atoms such as iodine, sulfur, nitrogen, and phosphorus. Among these, diaryliodonium salts and triarylsulfonium salts are preferred. These can be used individually or in combination depending on the curing temperature and curing time.

[0201] The amount of these polymerization initiators for thermosetting resins used is usually 0.001% by mass or more, more preferably 0.01% by mass or more, and usually 50% by mass or less, more preferably 10% by mass or less, relative to the matrix resin. If the amount of these polymerization initiators for thermosetting resins is excessively low, the concentration of the polymerization initiator will be too low, which may cause the polymerization reaction to take too long. On the other hand, if the amount of polymerization initiators for thermosetting resins is excessively high, the polymerization reaction may not produce a continuous ring-opening reaction.

[0202] <Isocyanate> As for the isocyanate, one having two or more isocyanate groups in one molecule is preferred, but the type is not particularly limited. If the number of isocyanate groups in one molecule is too small, the required hardness for the matrix resin may not be obtained. There is no particular upper limit to the number of isocyanate groups in one molecule, but it is usually 8 or less, and more preferably 4 or less. If the number of isocyanate groups in one molecule is too large, it may take a long time to consume the isocyanate groups, and the formation of the matrix resin may take too long. There is no particular upper limit to the number of isocyanate groups in one 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'-methylenebis(cyclohexyl isocyanate); aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene-1,5'-diisocyanate; and polymers thereof, with 3 to 7-mers being preferred.

[0204] In addition, other examples include reaction products of water, polyhydric alcohols such as trimethylolethane and trimethylolpropane with the above-mentioned isocyanates, as well as polymers or derivatives of hexamethylene diisocyanate. The molecular weight of the isocyanate is preferably 100 to 50,000 in number average molecular weight, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is excessively small, the crosslinking density will increase, which may cause the hardness of the matrix resin to become too high and reduce the recording speed. Conversely, if the number average molecular weight is excessively large, the compatibility with other components will decrease and the crosslinking density will decrease, which may cause the hardness of the matrix resin to become too low and result in the loss of recorded data.

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

[0206] (Polypropylene polyol) Polypropylene polyols are obtained by the reaction of propylene oxide with a diol or polyhydric alcohol. Examples of diols or polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol. Commercially available polypropylene polyols include Sannix GP-400 and GP-1000 (both manufactured by Sanyo Chemical Industries, Ltd., trade names), and Adeka Polyether G400, G700, and G1500 (all manufactured by ADEKA Corporation, trade names).

[0207] (Polycaprolactone polyol) Polycaprolactone polyols are obtained by the reaction of a lactone with a diol or polyhydric alcohol. 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 polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol.

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

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

[0211] Examples of dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, and trimellitic acid.

[0212] Examples of polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol.

[0213] Examples of polyester polyols include polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. Commercially available polyester polyols include ADEKA New Ace F series, ADEKA New Ace Y series, ADEKA New Ace NS series (manufactured by ADEKA Corporation, product names), and Kuraray Polyol N-2010, P-4011, P-1020 (all manufactured by Kuraray Co., Ltd., product names).

[0214] (Polycarbonate polyol) Examples of polycarbonate polyols include those obtained by de-alcoholization condensation reactions between glycols and dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, etc.), those obtained by de-phenolization condensation reactions between glycols and diphenyl carbonates, and those obtained by de-glycolization condensation reactions between glycols and carbonates (e.g., ethylene carbonate, diethyl carbonate, etc.).

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

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

[0217] Examples of commercially available polycarbonate polyols include Praxel CD CD205, Praxel CD CD210, Praxel CD CD220 (all manufactured by Daicel Corporation, product names), and Duranol T5651, Duranol T5652, Duranol T5650J (all manufactured by Asahi Kasei Corporation, product names).

[0218] (Molecular weight of polyols) The molecular weight of the polyol described above is preferably 100 to 50,000 in number average molecular weight, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is excessively small, the crosslinking density will increase, which may cause the hardness of the matrix resin to become too high and reduce the recording speed. Conversely, if the number average molecular weight is excessively large, the compatibility with other components may decrease or the crosslinking density may decrease, which may cause the hardness of the matrix resin to become too low and result in the loss of recorded data.

[0219] <Other ingredients> The matrix resin in this embodiment may contain other components in addition to the components described above, as long as it does not contradict the spirit of the present invention.

[0220] Other such components include, for example, compounds having hydroxyl groups, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, trimethylolpropane, polyethylene glycol, and polytetramethylene glycol, which are used to alter the physical properties of the matrix resin.

[0221] <Urethane polymerization catalyst> To promote the reaction between the isocyanate and the polyol, a suitable urethane polymerization catalyst may be included. Examples of urethane polymerization catalysts include onium salts such as bis(4-t-butylphenyl)iodonium perfluoro-1-butanesulfonic acid, bis(4-t-butylphenyl)iodonium p-toluenesulfonic acid, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonic acid, (4-bromophenyl)diphenylsulfonium triflate, (4-t-butylphenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyliodonium perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium trifluoromethanesulfonic acid, bis(alkylphenyl)iodonium hexafluorophosphonic acid, zinc chloride, tin chloride, iron chloride, aluminum chloride, Examples of catalysts include those primarily composed of Lewis acids such as BF3, 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-undecylimidazolium trimellitic acid, bases such as sodium hydroxide, potassium hydroxide, and potassium carbonate, tin catalysts such as dibutylsus laurate, dioctylsusus laurate, and dibutyltin octoate, bismuth catalysts such as tris(2-ethylhexanoate)bismuth and tribenzoyloxybismuth, and zirconium catalysts such as tetrakis(ethylacetoacetate)zirconium, 1,1'-isopropylidenezirconocene dichloride, and tetrakis(2,4-pentanedionato)zirconium.

[0222] In particular, bismuth catalysts and zirconium catalysts are preferred for improving storage stability.

[0223] The bismuth-based catalyst is not particularly limited as long as it is a catalyst containing the element bismuth and is a compound that promotes the reaction between isocyanates and polyols. Examples of bismuth-based catalysts include tris(2-ethylhexanoate)bismuth, tribenzoyloxybismuth, bismuth triacetate, tris(dimethyldiocerbamic acid)bismuth, bismuth hydroxide, triphenylbismuth(V)bis(trichloroacetate), tris(4-methylphenyl)oxobisobismuth(V), and triphenylbis(3-chlorobenzoyloxy)bismuth(V).

[0224] Among these, trivalent bismuth compounds are preferred from the viewpoint of catalytic activity, and bismuth carboxylates, represented by the general formula Bi(OCOR)3 (where R is a linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aromatic group), are more preferred. Any one of the above bismuth-based catalysts may be used alone, or two or more may be used in any combination and ratio.

[0225] The zirconium-based catalyst is not particularly limited as long as it is a catalyst containing the element zirconium and is a compound that promotes the reaction between isocyanates and polyols. Examples include cyclopentadienylzirconium trichloride, decamethylzirconocene dichloride, 1,1'-dibutylzirconocene dichloride, 1,1'-isopropylidenezirconocene dichloride, tetrakis(2,4-pentanedionato)zirconium, tetrakis(trifluoro-2,4-pentanedionato)zirconium, tetrakis(hexafluoro-2,4-pentanedionato)zirconium, zirconium butoxide, zirconium Examples include nium-t-butoxide, zirconium propoxide, zirconium isopropoxide, zirconium ethoxide, bis(ethylacetate)dibutoxyzirconium, tetrakis(ethylacetate)zirconium, zirconium oxide, barium zirconium oxide, calcium zirconium oxide, zirconium bromide, zirconium chloride, zirconium fluoride, (indenyl)zirconium chloride, and zirconium carbonate.

[0226] Among these, compounds having organic ligands are preferred in terms of compatibility with other components, and are preferred over compounds having an alkoxide or acetylacetonate (2,4-pentanedionate) structure. Any one of the above zirconium compounds may be used alone, or two or more may be used in any combination and ratio.

[0227] The bismuth-based catalyst and the zirconium-based catalyst may be used individually or in combination.

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

[0229] While curing can be achieved at room temperature using a urethane polymerization catalyst, curing may also be performed at a higher temperature. The preferred temperature for this is between 40°C and 90°C.

[0230] 6-1-3. Photocurable resin When using a photocurable resin as the matrix resin, it is necessary to cure it using a photoinitiator for matrix resins appropriate to the wavelength used. Since curing during light irradiation can interfere with molding and bonding, it is desirable that the curing reaction be stable at room temperature, which is the main working temperature. Considering this, catalytic curing using a photoinitiator for matrix resins is a desirable choice.

[0231] Generally, photoinitiators for matrix resins generate either cationic or anionic active substrates upon light irradiation. Therefore, it is considered best to select a photoinitiator that undergoes curing due to these active substrates and then cure it to produce the matrix resin.

[0232] Examples of functional groups that react with cations such as protons include epoxy groups and oxetanyl groups. Specifically, compounds having these include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerin, alicyclic epoxy compounds having 4- to 7-membered ring cyclic aliphatic groups such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and phenol or cresol novolac type epoxy compounds. Examples of compounds having an oxetanyl group include 2-ethyl-2-oxetanyl ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetanyloxy)hexane. (Note that the terms "(poly)ethylene glycol" used here refer to both "ethylene glycol" and its polymer, "polyethylene glycol.")

[0233] Examples of functional groups that react with anions include epoxy groups and episulfide groups. Specific examples of compounds containing episulfide groups include phenyl episulfide and diepisulfide methyl ether of bisphenol A.

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

[0235] Furthermore, especially when used as a holographic recording material, light is irradiated during recording, so it is important that the wavelength of curing and the wavelength of recording are different. The difference in wavelength should be at least 10 nm, preferably 30 nm. The selection of a photoinitiator for the matrix resin can generally be predicted from the absorption wavelength of the initiator.

[0236] 6-2. Photopolymerization Initiators Any known photoradical polymerization initiator can be used to assist in the polymerization of the compounds of the present invention. Examples include azo compounds, azide compounds, organic peroxides, organic borates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, oxime esters, and the like. Among these, titanocene compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred as photopolymerization initiators because the polymerization reaction occurs with visible light.

[0237] 6-2-1. Titanocene Compounds When using a titanocene compound as a photopolymerization initiator, the type is not particularly limited, but it can be appropriately selected and used from among the various titanocene compounds described in, for example, Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197.

[0238] Specific examples of titanocene compounds include dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, and dicyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-yl Examples include dicyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, and dicyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyri-1-yl)-phenyl-1-yl.

[0239] 6-2-2. Acylphosphine Oxide Compounds Specific examples of acylphosphine oxide compounds include monofunctional initiators that have only one photocatalytic cleavage site per molecule, and bifunctional initiators that have two photocatalytic cleavage sites per molecule.

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

[0241] Examples of bifunctional 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-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)ethanone, 4-(acetoxyimino)-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-5-methyl oxopentanoate, 1-(9-ethyl-6-cyclohexanoyl-9H-carbazole-3-yl)-1-(O-acetyloxime)methyl glutarate, 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetyloxime)methyl glutarate, and 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetyloxime)-3-methylbutanoic acid.

[0243] 6-2-4. Amount of photopolymerization initiator to be used The above-mentioned photopolymerization initiators may be used individually or in combination of two or more in any combination and ratio.

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

[0245] If the amount of photopolymerization initiator is too low, the amount of radicals generated will be small, which will slow down the photopolymerization rate and may result in a decrease in the recording sensitivity of the holographic recording medium. On the other hand, if the amount of photopolymerization initiator is too high, the radicals generated by light irradiation may recombine or become disproportionate, reducing their contribution to photopolymerization and potentially lowering the recording sensitivity of the holographic recording medium. When using two or more photopolymerization initiators in combination, it is preferable that their total amount satisfy the above range.

[0246] 6-3. Radical scavengers In holographic recording, radical scavengers may be added to accurately fix the interference light intensity pattern as a polymer distribution in the holographic recording medium. The radical scavenger preferably has both a functional group that captures radicals and a reactive group that is covalently fixed to the matrix resin. A stable nitroxyl radical group is an example of a functional group that captures radicals.

[0247] 6-3-1. Types of radical scavengers Examples of reactive groups that can be covalently immobilized on the matrix resin include hydroxyl groups, amino groups, isocyanate groups, and thiol groups. Examples of such radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxyl, and 5-HO-AZADO:5-hydroxy-2-azabicyclo[3.3.1.1] 3,7 Decane N-oxyl is one example.

[0248] 6-3-2. Radical scavenger content The various radical scavengers described above may be used individually or in combination of two or more in any combination and ratio. The content of the radical scavenger in the polymerizable composition of the present invention is preferably 0.5 μmol / g or more, and more preferably 1 μmol / g or more, in molar amount per unit weight of the polymerizable composition. Furthermore, the content of the radical scavenger in the polymerizable composition of the present invention is preferably 100 μmol / g or less, and more preferably 50 μmol / g or less.

[0249] If the radical scavenger content is too low, the efficiency of radical scavenging decreases, and a large amount of low-molecular-weight polymer tends to diffuse, resulting in a higher proportion of components that do not contribute to the signal. On the other hand, if the radical scavenger content is too high, the polymerization efficiency of the polymer decreases, and signal recording tends to become impossible. When using two or more radical scavengers in combination, it is preferable that their total amount satisfies the above range.

[0250] 6-4. Other ingredients The polymerizable composition of the present invention may contain other components in addition to the components described above, as long as this does not contradict the spirit of the present invention.

[0251] Other components include solvents, plasticizers, dispersants, leveling agents, defoamers, and adhesion promoters for preparing polymerizable compositions, and, especially when used in holographic recording media, chain transfer agents, polymerization inhibitors, compatibilizers, reaction aids, and sensitizers for controlling the recording reaction. Examples of other additives that may be necessary for improving properties include preservatives, stabilizers, antioxidants, UV absorbers, and light stabilizers. These components may be used individually or in any combination and ratio of two or more.

[0252] <Sensitizer> The polymerizable composition of the present invention may contain compounds that control the excitation of the photopolymerization initiator. Examples of such compounds include sensitizers and sensitizing aids.

[0253] As a sensitizer, any sensitizer can be selected and used from among various known sensitizers. Generally, colored compounds such as dyes are often used as sensitizers to absorb visible and ultraviolet laser light. When used in holographic recording media, depending on the wavelength of the laser light used for recording and the type of initiator used, in the case of a system using a green laser, specific examples of preferred sensitizers include compounds described in Japanese Patent Publication No. 5-241338, Japanese Patent Publication No. 2-69, Japanese Patent Publication No. 2-55446, etc. In the case of a system using a blue laser, examples of compounds described in Japanese Patent Publication No. 2000-10277, Japanese Patent Publication No. 2004-198446, etc. These sensitizers may be used individually or in combination of two or more in any combination and ratio.

[0254] When the resulting holographic recording medium is required to be colorless and transparent, it is preferable to use a cyanine-based dye as a sensitizer. Since cyanine-based dyes are generally easily decomposed by light, post-exposure, i.e., leaving the recording medium under indoor light or sunlight for several hours to several days, decomposes the cyanine-based dye in the holographic recording medium, causing it to lose absorption in the visible range, and a colorless and transparent holographic recording medium is obtained.

[0255] The amount of sensitizer needs to be increased or decreased depending on the thickness of the recording layer to be formed, but it is preferable to use a ratio of 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 10% by mass or less, more preferably 5% by mass or less, as described in 6-2. Photopolymerization initiator. If the amount of sensitizer used is too little, the initiation efficiency will decrease, and recording may take a considerable amount of time. On the other hand, if the amount of sensitizer used is too much, the absorption of light used for recording and playback will increase, and it may become difficult for light to penetrate in the depth direction. When using two or more sensitizers in combination, their total amount should satisfy the above range.

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

[0257] Examples of plasticizers include phthalate esters such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and diundecyl phthalate; adipate esters such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate; sebacate esters such as dioctyl sebacate and dibutyl sebacate; phosphate esters such as tricresyl phosphate; citrate esters such as tributyl acetyl citrate; trimellitic acid esters such as trioctyl trimellitic acid; alkoxylated (poly)alkylene glycol esters such as epoxidized soybean oil, chlorinated paraffin, and acetoxymethoxypropane; and terminally alkoxylated polyalkylene glycols such as dimethoxypolyethylene glycol.

[0258] Plasticizers containing a fluorine element, as exemplified in Japanese Patent Publication No. 6069294, can also be used. Examples of plasticizers containing a fluorine element include 2,2,2-trifluoroethylbutylcarbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl)biscarbamate, bis(2,2,2-trifluoroethyl)-[4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl]biscarbamate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylbutylcarbamate, and 2,2,2-trifluoroethylphenylcarbamate.

[0259] These plasticizers are typically used in a ratio of 0.01% to 50% by mass, preferably 0.05% to 20% by mass, relative to the total solid content of the polymerizable composition. If the plasticizer content is lower than this range, the effect of improving reaction efficiency and adjusting physical properties will not be achieved, and if it is higher, the transparency of the recording layer will decrease or plasticizer bleed-out will become significant.

[0260] <Leveling agent> Leveling agents can be used in the polymerizable composition of the present invention. Examples of leveling agents include sodium polycarboxylate salts, ammonium polycarboxylate salts, amine polycarboxylate salts, silicon-based leveling agents, acrylic-based leveling agents, ester compounds, ketone compounds, and fluorine compounds. These may be used individually or in any combination and ratio of two or more.

[0261] <Chain movement agent> Chain transfer agents can be used in the polymerizable composition of the present invention. Examples of chain transfer agents include phosphinates such as sodium phosphite and sodium hypophosphite, mercaptans such as mercaptoacetic acid, mercaptopropionic acid, 2-propanethol, 2-mercaptoethanol, and thiophenol, aldehydes such as acetaldehyde and propionaldehyde, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as trichloroethylene and perchloroethylene, terpenes such as terpinolene, α-terpinene, β-terpinene, and γ-terpinene, 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, and 1,4-hep Examples include non-conjugated dienes such as tadiene, 1,4-hexadiene, 2-methyl-1,4-pentadiene, 3,6-nonanediene-1-ol, and 9,12-octadecadienol; linolenic acids such as linolenic acid, γ-linolenic acid, methyl linolenate, ethyl linolenate, isopropyl linolenate, and linolenic anhydride; linoleic acids such as linoleic acid, methyl linoleate, ethyl linoleate, isopropyl linoleate, and linoleic anhydride; eicosapentaenoic acids such as eicosapentaenoic acid and ethyl eicosapentaenoate; and docosahexaenoic acids such as docosahexaenoic acid and ethyl docosahexaenoate.

[0262] The amount of these additives used is preferably in the range of 0.001% by mass or more, more preferably 0.01% by mass or more, and usually 30% by mass or less, more preferably 10% by mass or less, relative to the total solid content of the polymerizable composition of this embodiment. When two or more additives are used in combination, their total amount should satisfy the above range.

[0263] 6-5. Composition ratio of each component in polymerizable compositions The content of each component in the polymerizable composition of the present invention is arbitrary, as long as it does not contradict 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 polymerizable composition.

[0264] The polymerizable compound content, including 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 polymerizable compound content is preferably 1000 μmol / g or less, more preferably 500 μmol / g or less, and even more preferably 300 μmol / g or less. When the polymerizable compound content is above the lower limit, sufficient diffraction efficiency can be obtained in the holographic recording medium, and when it is below the upper limit, compatibility with the resin matrix in the recording layer is maintained, and shrinkage of the recording layer due to recording tends to be kept low.

[0265] When isocyanate and polyol are used as the matrix resin in the polymerizable composition of the present invention, their combined content is usually 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less. By setting this content above the lower limit mentioned above, it becomes easier to form the recording layer.

[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 higher, more preferably 0.5 or higher, typically 10.0 or lower, and preferably 2.0 or lower. When this ratio falls within the above range, there are fewer unreacted functional groups, and storage stability is improved.

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

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

[0269] 6-6. Method for producing polymerizable compositions In the present invention, the method for producing a polymerizable composition comprising a polymerizable compound, a matrix resin, and a photopolymerization initiator is not particularly limited, and the mixing order and other factors can be adjusted as appropriate. Furthermore, if the polymerizable composition contains components other than those mentioned above, the components may be mixed in any combination and order.

[0270] When using isocyanate and polyol as the matrix resin, polymerizable compositions can be obtained, for example, by the following methods, but the present invention is not limited thereto. A photoreactive composition (Solution A) is prepared by mixing a polymerizable compound and a photopolymerization initiator with all components except the isocyanate and urethane polymerization catalyst. Solution B is prepared by mixing the isocyanate and urethane polymerization catalyst. Alternatively, all components except the isocyanate can be mixed with the polymerizable compound and the photopolymerization initiator to form a photoreactive composition (Solution A).

[0271] It is preferable to dehydrate and degas each liquid. If dehydration and degassing are insufficient, air bubbles may form during the preparation of the hologram recording medium, making it impossible to obtain a uniform recording layer. Heating and reduced pressure may be used during dehydration and degassing, as long as the individual components are not damaged.

[0272] The polymerizable composition, obtained by mixing liquid A and liquid B, is preferably prepared immediately before molding the hologram recording medium. Conventional mixing techniques can also be used. Furthermore, during the mixing of liquid A and liquid B, degassing may be performed as needed to remove residual gas. Additionally, it is preferable that liquids A and B undergo a filtration process to remove foreign matter and impurities, either individually or after mixing, and it is more preferable to filter each liquid separately.

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

[0274] 6-7. Holographic recording medium of the present invention The holographic recording medium of the present invention, using the polymerizable composition of the present invention, comprises a recording layer and, optionally, a support or other layers. Typically, a holographic recording medium has a support, and the recording layer and other layers are laminated on this support to constitute the holographic recording medium. However, if the recording layer or other layers have the necessary strength and durability for the medium, the holographic recording medium does not need to have a support. Examples of other layers include a protective layer, a reflective layer, an anti-reflective layer (anti-reflective film), and the like.

[0275] 6-7-1. Recording Layer The recording layer of the hologram recording medium of the present invention is a layer formed from the polymerizable composition of the present invention, and is the layer on which information is recorded. The information is usually recorded as a hologram. As described later in the section on recording methods, the polymerizable compound (hereinafter referred to as polymerizable monomer) contained in the recording layer undergoes a chemical change such as polymerization due to hologram recording or the like. Therefore, in the hologram recording medium after recording, a portion of the polymerizable monomer is consumed and exists as a compound after the reaction, such as a polymer.

[0276] There are no particular restrictions on the thickness of the recording layer, and it can be determined appropriately considering the recording method, etc., but it is preferably 1 μm or more, more preferably 10 μm or more, and also preferably 1 cm or less, and even more preferably 3 mm or less. By setting the thickness of the recording layer to be above the lower limit, the selectivity of each hologram increases during multiplex recording on the holographic recording medium, and the degree of multiplex recording tends to increase. By setting the thickness of the recording layer to be below the upper limit, it becomes possible to form the entire recording layer uniformly, and multiplex recording tends to be possible with uniform diffraction efficiency of each hologram and a high S / N ratio.

[0277] The shrinkage rate of the recording layer due to exposure during information recording and playback is preferably 0.25% or less from the viewpoint of recording reproducibility.

[0278] 6-7-2.Support As long as the support has the necessary strength and durability for the holographic recording medium, there are no particular restrictions on its details, and any support can be used. There are no restrictions on the shape of the support, but it is usually formed in the form of a flat plate or film. There are no restrictions on the materials that make up the support structure; it can be transparent or opaque.

[0279] Examples of transparent materials for the support include organic materials such as acrylic, polyethylene terephthalate, polyethylene naphthoate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, polycycloolefin, and cellulose acetate; and inorganic materials such as glass, silicon, and quartz. Among these, polycarbonate, acrylic, polyester, amorphous polyolefin, and glass are preferred, and polycarbonate, acrylic, amorphous polyolefin, polycycloolefin, and glass are particularly preferred.

[0280] Opaque materials for the support include metals such as aluminum, and transparent supports coated with metals such as gold, silver, or aluminum, or dielectrics such as magnesium fluoride or zirconium oxide.

[0281] There are no particular restrictions on the thickness of the support, but it is preferable to have a thickness in the range of 0.05 mm or more and 1 mm or less. If the thickness of the support is greater than or equal to the lower limit, the mechanical strength of the hologram recording medium can be obtained and warping of the substrate can be prevented. If the thickness of the support is less than or equal to the upper limit, advantages such as increased light transmission and reduction in the weight and cost of the hologram recording medium can be obtained.

[0282] The surface of the support may be subjected to a surface treatment. This surface treatment is usually performed to improve the adhesion between the support and the recording layer. Examples of surface treatments include corona discharge treatment of the support or the formation of a primer layer on the support beforehand. Examples of primer layer compositions include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc.

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

[0284] These surface treatments may be applied to control the permeability of gases and moisture to the substrate. For example, by providing a support that suppresses the permeability of gases and moisture to the support sandwiching the recording layer, 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 hologram recording medium of the present invention, or on both sides. However, if the support is provided on both the upper and lower sides of the recording layer, at least one of the support members shall be made transparent so as to transmit active energy rays (excitation light, reference light, regeneration light, etc.).

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

[0287] The support may be provided with a pattern for data addresses. There are no restrictions on the method of patterning in this case, but for example, the support itself may have irregularities formed on it, a pattern may be formed on the reflective layer described later, or a combination of these methods may be used.

[0288] 6-7-3.Protective layer The protective layer is a layer designed to prevent deterioration of the recording and playback characteristics of the recording layer. There are no restrictions on the specific composition of the protective layer, and any known material can be arbitrarily applied. For example, a layer made of a water-soluble polymer, organic / inorganic material, 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 may be formed on the surface of the recording layer, between the recording layer and the support, or on the outer surface of the support. The protective layer may also be formed between the support and other layers.

[0290] 6-7-4. Reflective layer The reflective layer is formed when a 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 on the outer surface of the support, but it is usually preferable that it be between the support and the recording layer. Any known material can be used as the reflective layer; for example, a thin film of metal can be used.

[0291] 6-7-5.Anti-reflection coating In both transmissive and reflective holographic recording media, an anti-reflective coating may be provided on the side where the information light, reference light, and regeneration light enter and exit, or between the recording layer and the support. The anti-reflective coating improves the efficiency of light utilization and suppresses the generation of noise. Any known anti-reflective coating can be used.

[0292] 6-7-6. Method for Manufacturing Holographic Recording Media There are no limitations on the method for manufacturing the holographic recording medium of the present invention. For example, it can be manufactured by applying the polymerizable composition of the present invention onto a support without a solvent to form a recording layer. Any method can be used for application. Specific examples include the spray method, spin coating method, wire bar method, dip method, air knife coating method, roll coating method, and blade coating method, doctor roll coating method, etc.

[0293] When forming a recording layer, especially a thick recording layer, methods such as molding by placing the material in a mold or coating it onto a release film and then punching it out can be used. Alternatively, the polymerizable composition of the present invention may be mixed with a solvent or additive to prepare a coating solution, which can then be applied to a support and dried to form the recording layer. In this case as well, any coating method can be used; for example, the same method as described above can be employed.

[0294] There are no restrictions on the solvent used in the coating solution, but it is generally preferable to use a solvent that has sufficient solubility for the components used, provides good film properties, and does not damage the support such as a resin substrate. One solvent may be used alone, or two or more solvents may be used in any combination and ratio. There are also no restrictions on the amount of solvent used. However, from the standpoint of coating efficiency and ease of handling, it is preferable to prepare a coating solution with a solid content concentration of about 1 to 100% by mass.

[0295] Examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, propanol, n-butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketone 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; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; 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. Examples include propylene glycol solvents such as cellulose monobutyl ether acetate and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate ethyl acetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and methyl 3-methoxypropionate; perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol; highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; linear 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 thereof.

[0296] Examples of methods for manufacturing holographic recording media include a method in which a polymerizable composition melted by heat is applied to a support and cooled to solidify to form a recording layer; a method in which a liquid polymerizable composition is applied to a support and cured by thermal polymerization to form a recording layer; and a method in which a liquid polymerizable composition is applied to a support and cured by photopolymerization to form a recording layer.

[0297] The holographic recording media manufactured in this manner can take the form of a self-supporting slab or disk and can be used in three-dimensional image display devices, diffractive optical elements, large-capacity memory, and other applications. In particular, the holographic recording medium of the present invention using the polymerizable composition of the present invention has high refractive index modulation and is also useful as an AR glass light guide plate.

[0298] 6-7-7. Applications of Holographic Recording Media <For high-capacity memory applications> The writing (recording) and reading (reproduction) of information to and from the holographic recording medium of the present invention are both performed by irradiation with light.

[0299] When recording information, light capable of causing chemical changes in polymerizable monomers, i.e., polymerization and concentration changes, is used as object light (also called recording light).

[0300] For example, when recording information as a volumetric hologram, object light is shone onto the recording layer along with reference light, causing the object light and reference light to interfere within the recording layer. This interference light causes polymerization and concentration changes of polymerizable monomers within the recording layer, resulting in interference fringes that create refractive index differences within the recording layer. These interference fringes then record the information as a hologram within the recording layer.

[0301] When reproducing a volume hologram recorded in a recording layer, a predetermined reproduction beam (usually a reference beam) is irradiated onto the recording layer. The irradiated reproduction beam is diffracted according to the interference fringes. Since this diffracted light contains the same information as that of the recording layer, the information recorded in the recording layer can be reproduced by reading the diffracted light with an appropriate detection means.

[0302] The wavelength ranges of the object beam, reproduction beam and reference beam are arbitrary depending on the respective applications, and may be either the visible light range or the ultraviolet range. Preferable examples among these light beams include solid-state lasers such as ruby, glass, Nd-YAG, and Nd-YVO4; diode lasers such as GaAs, InGaAs, and GaN; gas lasers such as helium-neon, argon, krypton, excimer, and CO2; and lasers excellent in monochromaticity and directivity, such as dye lasers having a dye.

[0303] There are no restrictions on the irradiation dose of any of the object beam, reproduction beam and reference beam, and the irradiation dose is arbitrary as long as recording and reproduction are possible. When the irradiation dose is extremely low, the chemical change of the polymerizable monomer may be too incomplete to sufficiently exhibit the heat resistance and mechanical properties of the recording layer. Conversely, when the irradiation dose is extremely high, the components of the recording layer (the components of the polymerizable composition of the present invention) may deteriorate. Therefore, the irradiation dose of the object beam, reproduction beam and reference beam is usually 0.1 J / cm 2 to 20 J / cm 2 in accordance with the composition of the polymerizable composition of the present invention used for forming the recording layer, the type and blending amount of the photopolymerization initiator, and the like, and irradiation is performed within the following range.

[0304] Hologram recording methods include a polarization collinear hologram recording method, a reference beam incident angle multiplexing hologram recording method, and the like. When the hologram recording medium of the present invention is used as a recording medium, any recording method can provide good recording quality.

[0305] <For AR Glass Light Guide Plates> A volume hologram is recorded on the hologram recording medium of the present invention in the same manner as in the aforementioned large-capacity memory application.

[0306] For a volume hologram recorded on a recording layer, a predetermined regeneration light is shone onto the recording layer. The shone regeneration light undergoes diffraction according to the interference fringes. In this case, even if the wavelength of the regeneration light does not match the wavelength of the recording light, diffraction will occur if the interference fringes and the Bragg condition are met. Therefore, by recording the corresponding interference fringes according to the wavelength and incident angle of the regeneration light to be diffracted, diffraction can be induced for regeneration light across a wide wavelength range, thereby expanding the display color gamut of AR glasses.

[0307] By recording the corresponding interference fringes according to the wavelength and diffraction angle of the regenerated light, it is possible to guide the regenerated light incident from outside the holographic recording medium into the holographic recording medium, reflect, demultiplex, or reduce the regenerated light that has been guided inside the holographic recording medium, or emit the regenerated light that has been guided inside the holographic recording medium out to the outside of the holographic recording medium, thereby widening the field of view of the AR glasses.

[0308] The wavelength ranges of object light and regenerated light are arbitrary depending on the application and can be in either the visible light or ultraviolet region. Among these types of light, lasers, as mentioned above, are particularly suitable. Regenerated light is not limited to lasers, and display devices such as liquid crystal displays (LCDs) and organic electroluminescent displays (OLEDs) are also suitable.

[0309] There are no restrictions on the irradiation doses of object light, regeneration light, and reference light; the irradiation doses are arbitrary as long as recording and regeneration are possible. If the irradiation dose is extremely low, the chemical change of the polymerizable monomer may be incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully realized. Conversely, if the irradiation dose is extremely high, the components of the recording layer (components of the polymerizable composition of the present invention) may deteriorate. Therefore, the object light, regeneration light, and reference light are usually set to 0.1 J / cm², depending on the composition of the polymerizable composition of the present invention used to form the recording layer, the type and amount of photopolymerization initiator used, etc. 2 Above, 20J / cm 2 Irradiate within the following range.

[0310] 6-8. Performance indicators for holographic recording media The performance of a holographic recording medium is indicated by totalΔn, which is calculated using the sum of diffraction efficiencies across the entire multiplexing process. In the case of a transmission hologram, the diffraction efficiency of the hologram is given by the ratio of the intensity of the diffracted light to the sum of the transmitted light intensity and the diffracted light intensity. From the obtained diffraction efficiencies, Δn is calculated using the following formula from Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum across the entire multiplexing process is taken as totalΔn.

[0311]

number

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

[0313] For large-capacity memory, a higher totalΔn is preferable because it means more information can be stored per unit volume. Furthermore, for AR glasses applications, a higher totalΔn is preferable because it allows for brighter projected images to reach the eyes, reduces power consumption, and widens the field of view. [Examples]

[0314] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples without departing from its essence.

[0315] The synthesis methods for each compound are described in detail below, along with their chemical formulas, including the synthesis process.

[0316] [Raw materials used] The raw materials used in the examples and comparative examples are as follows:

[0317] <Isocyanate> • Duranate® TSS-100: Hexamethylene diisocyanate-based polyisocyanate (NCO 17.6%) (manufactured by Asahi Kasei Corporation)

[0318] <Polyol> • Praxel PCL-205U: Polycaprolactone diol (molecular weight 530) (manufactured by Daicel Corporation) • Praxel PCL-305: Polycaprolactone triol (molecular weight 550) (manufactured by Daicel Corporation)

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

[0320] <Radical scavenger> • TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) <Light stabilizer> • ADEKA stub LA-63P (manufactured by ADEKA Corporation)

[0321] <Urethane polymerization catalyst> • Octylic acid solution of tris(2-ethylhexanoate)bismuth (active ingredient content 56% by mass)

[0322] (Synthesis Example 1) Applying the method described in Japanese Patent Publication No. 2017-14213, bis(4-dibenzothiophenyl) disulfide was produced as compound S-1 and 4-dibenzothiophenthiol was produced as compound S-2 by the following synthesis method.

[0323] [ka]

[0324] 20 g of dibenzothiophene was dissolved in 300 mL of THF, and while cooling to 0°C, 74.6 mL of 1.6 M n-butyllithium hexane solution was added, the temperature was raised to 20°C, and the mixture was stirred for 2 hours. The resulting brown reaction solution was cooled to -40°C, and 3.8 g of sulfur (powdered, manufactured by Wako Pure Chemical Industries) was added. After stirring at -40°C for 30 minutes, 5 mL of water was added to the reaction solution to stop the reaction. The obtained solution was concentrated using an evaporator, the resulting solid was washed with 100 mL of toluene for 30 minutes, and the yellow solid was filtered off to produce compound S-1.

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

[0326] An appropriate amount of compound S-2 (approximately 10 mg) was dissolved in several mL of deuterated chloroform. If any insoluble matter remained, the solution was filtered using a cotton plug, and the solution was transferred to a dedicated sample tube and capped. Using this, the resonance state of hydrogen was measured using a 400 MHz nuclear magnetic resonance (NMR) spectrometer, and each resonance line was attributed to the hydrogen of the compound to confirm that the target product had been obtained. The measurement data is shown below. Similar measurements were performed for each of the target products described below to confirm that the target product had been obtained. The measurement data is 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 using the following synthesis method.

[0328] [ka]

[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. Potassium tert-butoxide (10.37 g) in a DMF (50 mL) solution was added dropwise at 75°C, and the mixture was stirred for 30 minutes.

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

[0331] The NMR measurement data for compound S-3 was as follows: 1 H-NMR(400MHz,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. 2-chloro-1,3-benzothiazole (1.34 g) was added dropwise over 1 hour at 30°C, followed by stirring for another hour. After the reaction was complete, the reaction mixture was poured 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 resulting crude product was purified by silica gel column chromatography to obtain 1.9 g of compound S-4 (yield 51%).

[0333] The NMR measurement data for compound S-4 was as follows: 1H 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. To this solution, 0.65 g of 2-isocyanatoethyl acrylate was added, and the mixture was reacted at room temperature for approximately 50 hours. After the reaction was complete, 20 mL of dichloromethane was added, and the mixture was passed through a silica gel short-pass column. The resulting solution was then 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 for 1 hour. The precipitate was filtered off, washed with methanol, and dried to obtain 1.6 g of compound M-1 (yield 71%).

[0335] The NMR measurement data for compound M-1 was as follows: 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] <Creation of holographic recording media> Solution A was prepared by dissolving 2.53 g of Duranate (registered trademark) TSS-100 with 0.269 g of compound M-1 as a polymerizable monomer, 0.0096 g of photopolymerization initiator HLI02, 3.30 mg of radical scavenger TEMPOL, and 2.6 mg of light stabilizer LA-63P. Separately, 1.73g of Praxel PCL-205U and 0.74g of Praxel PCL-305 were mixed (Praxel PCL-205U:Praxel PCL-305 = 70:30 (mass ratio)), and 0.2mg of octyolic acid solution of tris(2-ethylhexanoate)bismuth was dissolved in it to prepare solution B.

[0337] After degassing both solution A and solution B under reduced pressure at room temperature or 45°C for 2 hours, 2.39g of solution A and 2.11g of solution B were stirred and mixed, and then degassed under vacuum for several minutes. Next, a 0.5 mm thick spacer sheet was placed on two opposing edges of a glass slide, and the vacuum-degassed mixture was poured onto the slide. Another glass slide was then placed on top, the edges were secured with clips, and the slide was heated at 80°C for 24 hours to produce a holographic recording medium as an evaluation sample. This evaluation sample had a 0.5 mm thick recording layer formed between the glass slides acting as a cover.

[0338] This holographic recording medium was formulated with a ratio of 1.0 between the number of isocyanate groups in solution A and the number of isocyanate-reactive groups in solution B. It contained 58.3 μmol / g of polymerizable monomer, 3.05 μmol / g of photopolymerization initiator, and 3.05 μmol / g of radical scavenger.

[0339] [Hologram recording and evaluation methods] Using a holographic recording medium prepared as an evaluation sample, holographic recording and the holographic recording performance of the holographic recording medium were evaluated according to the procedure described below.

[0340] Holographic recording was performed using a semiconductor laser with a wavelength of 405 nm, with an exposure power density of 10.2 mW / cm² per beam. 2 Holographic recording of two-beam plane waves was performed using the exposure apparatus shown in Figure 1. The medium was rotated from -22.5° to 22.5°, and angle-multiplex recording was performed at the same location. The diffraction efficiency was measured for each multiplex recording. Δn was calculated from the obtained diffraction efficiencies, and the sum of the total Δn for all multiplex recordings was defined as totalΔn. The details are explained below.

[0341] (Holographic recording) Figure 1 is a schematic diagram showing the configuration of the equipment used for hologram recording. In Figure 1, S represents a sample of the holographic recording medium, and M1 to M3 all represent mirrors. PBS represents a polarizing beam splitter, and L1 represents a recording light laser source emitting light at a wavelength of 405 nm (a TOPTICA Photonics single-mode laser that produces light around 405 nm (labeled "L1" in Figure 1)). L2 represents a regeneration light laser source emitting light at a wavelength of 633 nm. PD1, PD2, and PD3 represent photodetectors. 1 represents an LED unit.

[0342] As shown in Figure 1, light with a wavelength of 405 nm was split by a polarizing beam splitter (labeled "PBS" in the figure), and the two beams were intersected on the recording surface so that the angle between them was 59.3°. At this time, the angle bisector of the two beams was made perpendicular to the recording surface, and furthermore, the oscillation plane of the electric field vectors of the two beams obtained by the splitting was made perpendicular to the plane containing the two intersecting beams.

[0343] After hologram recording, a He-Ne laser capable of producing light with a wavelength of 633 nm (V05-LHP151 from Meresglio: labeled "L2" in the figure) was used to irradiate the hologram recording medium with this light at a 50.7° angle. The diffracted light was then detected using a photodiode and a photosensor amplifier (S2281, C9329 from Hamamatsu Photonics: labeled "PD1" in the figure) to determine whether the hologram recording had been performed correctly.

[0344] (Measurement of diffraction efficiency) 151 multiplexed recordings were made, varying the angle at which the sample was moved relative to the optical axis (the angle between the angle bisector of the interior angle at the point where the incident light from mirrors M1 and M2 in Figure 1 intersect, and the normal from the sample) in 0.3° increments from -22.5° to 22.5°.

[0345] After multiplex recording, the remaining initiator and monomer were consumed by illuminating the LED unit (1 in the figure, center wavelength 405 nm) for a certain period of time. This process is called post-exposure. The LED power was 100 mW / cm². 2 The cumulative energy is 12 J / cm². 2 The irradiation was applied in such a manner that it resulted in the following:

[0346] The diffraction efficiency of a hologram is given by the ratio of the intensity of the diffracted light to the sum of the transmitted light intensity and the diffracted light intensity. Light from mirror M1 (wavelength 405 nm) in Figure 1 was shone on the hologram, and the diffraction efficiency was measured from an angle of -23° to 23°. From the obtained diffraction efficiencies, Δn was calculated using the following formula from Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum of these over the entire multiplexed recording was taken as totalΔn.

[0347]

number

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

[0349] Using multiple samples, we performed multiple evaluations with varying irradiation energy conditions, such as increasing or decreasing the initial irradiation energy and the total irradiation energy. We sought conditions that would almost completely consume the polymerizable monomer (where totalΔn would reach near equilibrium in multiple recordings), and selected the conditions that would maximize totalΔn. The obtained maximum value was then defined as the totalΔn for that medium.

[0350] (Measurement of transmittance before and after recording) The pre-recording transmittance was measured by measuring the ratio of transmitted light power to incident light power in the evaluation sample before recording. Furthermore, after hologram recording, the post-recording transmittance was measured by measuring the ratio of transmitted light power to incident light power in evaluation samples that were post-exposed.

[0351] (Measurement of haze after recording) Using evaluation samples that underwent hologram recording and post-exposure, the haze value for white light was measured using a haze meter NDH 7000SPII manufactured by Nippon Denshoku Industries Co., Ltd. (JIS K7136). Furthermore, the ratio of this haze value to the totalΔn (haze % / totalΔn) was calculated. A lower ratio indicates a higher level of balance between diffraction efficiency and transparency.

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

[0353] [ka]

[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 stirred for 4 hours while monitoring the reaction progress by TLC and HPLC analysis. After the mixture cooled to room temperature, 12.2 g of 2-bromobenzenethiol 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 off and washed with 100 mL of ethyl acetate. The resulting organic layer was concentrated, and the crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 12.4 g of compound S-5 (yield 88%).

[0355] The NMR measurement data for compound S-5 was as follows: 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-boronic acid (4.5g), and potassium phosphate (5.5g) were suspended in 20mL of toluene, 10mL of ethanol, and 10mL of water, and degassed by passing nitrogen gas through the solution. 138mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred under reflux for 6 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4g of activated carbon was added to the resulting organic layer and stirred for 30 minutes. After Celite filtration, the crude product was concentrated and purified using a silica gel column (hexane-ethyl acetate) to obtain 4.4g of crude compound S-6.

[0357] The NMR measurement data for compound S-6 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120°C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layer was concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 4.1 g of compound S-7 (yield 82%).

[0359] The NMR measurement data for compound S-7 was as follows: 1H 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 (5g) was dissolved in 15mL of dichloromethane, and 100mg of dibutyltin dilaurate was added. To this solution, 0.85g of 2-isocyanatoethyl acrylate (Showa Denko K.K., Karenz AOI) was added, and the reaction was carried out at room temperature. After 24 hours, 0.3g of 2-isocyanatoethyl acrylate was added, and the reaction was carried out for another 24 hours. After adding saturated sodium bicarbonate aqueous solution to the reaction solution, 50mL of chloroform was added, and the mixture was extracted. 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 3.6g of compound M-2 (yield 62%).

[0361] The NMR measurement data for compound M-2 was as follows: 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-2 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0364] [ka]

[0365] 10 g of bis(bromomethyl)oxetane, 16.3 g of 2-bromobenzenethiol, 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 stirred under reflux for 3 hours while monitoring the reaction progress by LC analysis. After cooling the mixture to room temperature, it was extracted twice with 600 mL of water and 300 mL of ethyl acetate. The resulting crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 26.5 g of compound S-5 (yield 96%). The NMR measurement data for the obtained compound S-5 was as shown above.

[0366] Compound S-5 (9g), thianthrene-1-boronic acid (11.2g), dichlorobis[triphenylphosphino]palladium(II) 1.37g, and potassium hydroxide (11g) were suspended in 90mL of tetrahydrofuran and 23mL of water, and degassed by passing nitrogen gas through the solution. Under a nitrogen atmosphere, the reaction solution was heated to 80°C and stirred for 12 hours. After cooling to room temperature, 125mL of ethyl acetate was added, and the mixture was extracted with 250mL of water. After concentrating the mixture with the organic layer from another lot that had undergone a similar reaction, the resulting crude product was purified using a silica gel column (heptane-ethyl acetate) to obtain 16g of compound S-8 (yield 66%).

[0367] The NMR measurement data for compound S-8 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120°C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layers were concentrated. The resulting crude product was purified by silica gel column (hexane·ethyl acetate) to obtain 10.3 g of compound S-9 (yield 88%).

[0369] The NMR measurement data for compound S-9 was as follows: 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. 2-Isocyanatoethyl acrylate (1.1 g) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, 0.5 g of 2-isocyanatoethyl acrylate was added, and the reaction was continued for another 24 hours. Saturated sodium bicarbonate aqueous solution was added to the reaction solution, followed by 50 mL of chloroform, and the mixture was extracted. 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 5.1 g of compound M-3 (70% yield).

[0371] The NMR measurement data for compound M-3 was as follows: 1H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-3 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0374] [ka]

[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 stirred for 4 hours while monitoring the reaction progress by TLC analysis. After the mixture cooled to room temperature, 11.6 g of 3-bromobenzenethiol 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 off and washed with 100 mL of ethyl acetate. The resulting organic layer was concentrated. The crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 11.8 g of compound S-10 (yield 83%).

[0376] The NMR measurement data for compound S-10 was as follows: 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-boronic acid (3.9 g), and potassium phosphate (4.6 g) were suspended in 20 mL of toluene, 10 mL of ethanol, and 10 mL of water, and degassed by passing nitrogen gas through the solution. 31 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred under reflux for 6 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the resulting organic layer and stirred for 30 minutes. After Celite filtration, the crude product was concentrated and purified using a silica gel column (hexane-ethyl acetate) to obtain 2.9 g of crude compound S-11.

[0378] The NMR measurement data for compound S-11 was as follows: 1 H 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. Under a nitrogen atmosphere, the reaction solution was heated to 120 °C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layer was concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 2.8 g of compound S-12 (yield 76%).

[0380] The NMR measurement data for compound S-12 was as follows: 1H 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. To this solution, 0.55 g of 2-isocyanatoethyl acrylate (Showa Denko K.K., Karenz AOI) was added, and the reaction was carried out at room temperature. After 24 hours, 0.2 g of 2-isocyanatoethyl acrylate was added, and the reaction was carried out for another 24 hours. After adding saturated sodium bicarbonate aqueous solution to the reaction solution, 50 mL of chloroform was added, and the mixture was extracted. 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 of compound M-4 (yield 48%).

[0382] The NMR measurement data for compound M-4 was as follows: 1 H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-4 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0385] [ka]

[0386] 20 g of bis(bromomethyl)oxetane, 32.6 g of 3-bromobenzenethiol, 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 stirred under reflux for 3 hours while monitoring the reaction progress by LC analysis. After cooling the mixture to room temperature, it was extracted twice with 600 mL of water and 300 mL of ethyl acetate. The resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 35 g of compound S-10 (yield 94%). The NMR measurement data of the obtained compound S-10 is as shown above.

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

[0388] The NMR measurement data for compound S-13 was as follows: 1 H 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. Under a nitrogen atmosphere, the reaction solution was heated to 110°C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, 100 mL of toluene was added and the mixture was washed with 1 M aqueous sodium hydroxide solution. The organic layer was then washed with 0.1 N hydrochloric acid and washed again with water. The insoluble matter in the organic layer was dissolved with chloroform, dried over anhydrous magnesium sulfate, and concentrated. The resulting crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 7.9 g of compound S-14 (yield 76%).

[0390] The NMR measurement data for compound S-14 was as follows: 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. 2-Isocyanatoethyl acrylate (1.1 g) was added to this 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 resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 3.6 g of compound M-5 (80% yield).

[0392] The NMR measurement data for compound M-5 was as follows: 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-5 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0395] [ka]

[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 off, washed with methanol, and dried under reduced pressure to obtain 1.3 g of compound S-15.

[0397] The NMR measurement data for compound S-15 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120 °C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layers were concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 5.5 g of compound S-16 (yield 78%).

[0399] The NMR measurement data for compound S-16 was as follows: 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. To this solution, 2-isocyanatoethyl acrylate (0.98 g) was added, and the mixture was reacted at 30°C for 30 hours. After the reaction was complete, the solution was concentrated at a temperature below 30°C, and the resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 2.0 g of compound M-6 (70% yield).

[0401] The NMR measurement data for compound M-6 was as follows: 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-6 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0404] [ka]

[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 (diglyme). The reaction mixture was heated to 120°C and stirred for 3 hours. After cooling to room temperature, the resulting white solid was filtered off, washed with methanol, and dried under reduced pressure to obtain 1.3 g of compound S-17 (yield 76%).

[0406] The NMR measurement data for compound S-17 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120 °C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layers were concentrated. The resulting crude product was washed with a small amount of methanol to obtain 6.9 g of compound S-18 (yield 94%).

[0408] The NMR measurement data for compound S-18 was as follows: 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. 2-isocyanatoethyl acrylate (1.0 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 3.4 g of compound M-7 (yield 72%).

[0410] The NMR measurement data for compound M-7 was as follows: 1H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-7 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0413] [ka]

[0414] Under controlled atmosphere, compound S-3 (2.0 g) obtained in Example 1 was dissolved in 8 mL of tetrahydrofuran, and 32 mL of dichloromethane and 26 mg of dibutyltin diacetate were added. 1.3 g of 2-bromobenzene isocyanate was added to this solution in three equal parts, and the mixture was reacted at an internal temperature of 5°C for 5 hours. After the reaction was complete, the solvent was removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain 1.85 g of compound S-19 (yield 68%).

[0415] The NMR measurement data for compound S-19 was as follows: 1H 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 passing nitrogen gas through the solution. 34 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it 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 over anhydrous magnesium sulfate. This solution was concentrated, and the resulting crude product was purified by silica gel column chromatography to obtain 1.8 g of compound S-20 (yield 89%).

[0417] The NMR measurement data for compound S-20 was as follows: 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. To this solution, 0.42 g of 2-isocyanatoethyl acrylate was added, and the mixture was reacted at room temperature for approximately 72 hours. After the reaction was complete, the mixture was purified using a silica gel column (dichloromethane / ethyl acetate), and the resulting 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 for 1 hour. The precipitate was filtered off, washed with methanol, and dried to obtain 1.2 g of compound M-8 (yield 68%).

[0419] The NMR measurement data for compound M-8 was as follows: 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-8 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0422] [ka]

[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-bromobenzenethiol and 9.2 g of potassium carbonate were added. The mixture was reacted under reflux conditions for 4 hours. After cooling to room temperature and adding water, the solution was extracted with ethyl acetate, washed with 1N sodium hydroxide solution, and then washed with a brine. The resulting solution was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (dichloromethane, ethyl acetate) to obtain 13.4 g of compound S-21 (yield 89%).

[0424] The NMR measurement data for compound S-21 was as follows: 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-bromobenzene isocyanate was added to this solution in three equal parts, and the reaction was allowed to proceed at room temperature for 7 hours. Water was added to stop the reaction, and after liquid-liquid extraction, 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 vacuum distillation. The crude product was purified using a silica gel column (dichloromethane, ethyl acetate) to obtain 3.4 g of compound S-22 (yield 47%).

[0426] The NMR measurement data for compound S-22 was as follows: 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 (3.3g), dibenzothiophene-4-boronic acid (3.7g), and potassium phosphate (3.6g) were suspended in 24mL of toluene, 24mL of ethanol, and 12mL of water, and degassed by passing nitrogen gas through the solution. 101mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred under reflux for 2 hours. After cooling to room temperature, it 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 over anhydrous magnesium sulfate. This solution was concentrated, and the resulting crude product was purified by silica gel column (dichloromethane, ethyl acetate) to obtain 4.1g of compound S-23 (yield 88%).

[0428] The NMR measurement data for compound S-23 was as follows: 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. To this solution, 0.97 g of 2-isocyanatoethyl acrylate was added, and the mixture was reacted at room temperature for approximately 72 hours. After the reaction was complete, the mixture was purified using a silica gel column (dichloromethane, ethyl acetate), and the resulting 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 for 2 hours. The precipitate was filtered off, washed with methanol, and dried to obtain 3.4 g of compound M-9 (yield 72%).

[0430] The NMR measurement data for compound M-9 was as follows: 1 H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-9 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0433] [ka]

[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-bromobenzene isocyanate was added to this solution in three equal parts, and the reaction was allowed to proceed at room temperature for 12 hours. Water was added to stop the reaction, and after liquid-liquid extraction, 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 vacuum distillation. The crude product was purified using a silica gel column (dichloromethane, ethyl acetate) to obtain 2.7 g of compound S-24 (yield 64%).

[0435] The NMR measurement data for compound S-24 was as follows: 1H 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 passing nitrogen gas through the solution. 82 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred under reflux for 2 hours. After cooling to room temperature, it 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 over anhydrous magnesium sulfate. This solution was concentrated, and the resulting crude product was purified by silica gel column (dichloromethane, ethyl acetate) to obtain 3.4 g of compound S-25 (yield 85%).

[0437] The NMR measurement data for compound S-25 was as follows: 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. To this solution, 0.63 g of 2-isocyanatoethyl acrylate was added, and the mixture was reacted at room temperature for approximately 72 hours. After the reaction was complete, the mixture was purified using a silica gel column (dichloromethane, ethyl acetate), and the resulting 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 for 2 hours. The precipitate was filtered off, washed with methanol, and dried to obtain 2.9 g of compound M-10 (yield 89%).

[0439] The NMR measurement data for compound M-10 was as follows: 1 H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-10 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0442] [ka]

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

[0444] The NMR measurement data for compound S-26 was as follows: 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 carbonyldiimidazole was added. After reacting at room temperature for 3 hours, water was added to stop the reaction, and after liquid-liquid extraction, the organic layer was washed with 0.1 N hydrochloric acid. Further, after brine washing and washing with water, it was dried over anhydrous magnesium sulfate. After concentration, the obtained crude product was purified by silica gel column (dichloromethane, ethyl acetate) to obtain 5.2 g of compound S-27 (yield 79%).

[0446] The NMR measurement data for compound S-27 was as follows: 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 over anhydrous magnesium sulfate. The crude product obtained after concentration was purified by silica gel column chromatography (dichloromethane, ethyl acetate) to obtain 1.7 g of compound S-28 (yield 87%).

[0448] The NMR measurement data for compound S-28 was as follows: 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 (1.7g), dibenzothiophene-4-boronic acid (1.2g), and potassium phosphate (1.1g) were suspended in 11mL of toluene, 11mL of ethanol, and 5mL of water, and degassed by passing nitrogen gas through the solution. 45mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 4 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with 1N sodium hydroxide aqueous solution. Further washing with water and Brine was performed, and the organic layer was dried over anhydrous magnesium sulfate. This solution was concentrated, and the resulting crude product was purified by silica gel column (dichloromethane, ethyl acetate) to obtain 1.7g of compound S-29 (yield 84%).

[0450] The NMR measurement data for compound S-29 was as follows: 1H 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. To this solution, 0.46 g of 2-isocyanatoethyl acrylate was added, and the mixture was reacted at room temperature for approximately 72 hours. After the reaction was complete, the mixture was purified using a silica gel column (dichloromethane, ethyl acetate), and the resulting fraction was concentrated to a total volume of 10 g at a temperature below 30°C. This solution was added dropwise to 180 mL of ice-cold methanol and stirred for 2 hours. The precipitate was filtered off, washed with methanol, and dried to obtain 1.2 g of compound M-11 (yield 61%).

[0452] The NMR measurement data for compound M-11 was as follows: 1 H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-11 was used as the polymerizable monomer. The results are shown in Table 1 below.

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

[0455] [ka] 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 saturated sodium bicarbonate aqueous solution was added and the mixture was extracted twice with 50 mL of dichloromethane. The organic layer was dried over Glauber's salt, filtered, and concentrated. The resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 770 mg of compound M-12 (yield 54%).

[0456] The NMR measurement data for compound M-12 was as follows: 1 H 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 using the following synthesis method.

[0458] [ka]

[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 (diglyme). The reaction mixture was heated to 120°C and stirred for 3 hours. After cooling to room temperature, the resulting solid was filtered off, washed with ethyl acetate / hexane mixed solvent, and dried under reduced pressure to obtain 5.2 g of compound S-30.

[0460] The NMR measurement data for compound S-30 was as follows: 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 (3.5g), dibenzothiophene-4-boronic acid (2.8g), and potassium phosphate (5.2g) were suspended in 60mL of toluene, 30mL of ethanol, and 30mL of water, and degassed by passing nitrogen gas through the solution. 31mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it 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 resulting organic layer and stirred for 30 minutes. After Celite filtration, the solution was concentrated, and the resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 4.3g of compound S-31 (yield 90%).

[0462] The NMR measurement data for compound S-31 was as follows: 1H 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. Under a nitrogen atmosphere, the reaction solution was heated to 100°C and stirred for 5 minutes. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layers were concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 3.8 g of compound S-32 (yield 65%).

[0464] The NMR measurement data for compound S-32 was as follows: 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. 2-isocyanatoethyl acrylate (0.9 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 3.4 g of compound M-13 (78% yield).

[0466] The NMR measurement data for compound M-13 was as follows: 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 using the following synthesis method.

[0468] [ka]

[0469] 10 g of bis(bromomethyl)oxetane, 16.3 g of 4-bromobenzenethiol, 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 stirred under reflux for 3 hours while monitoring the reaction progress by LC analysis. After cooling the mixture to room temperature, it was extracted twice with 300 mL of water and 150 mL of ethyl acetate. The resulting crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 18.1 g of compound S-33 (yield 94%).

[0470] The NMR measurement data for compound S-33 was as follows: 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 (6.8g), thianthrene-1-boronic acid (8.5g), dichlorobis[triphenylphosphino]palladium(II) 1.04g, and potassium hydroxide (8.3g) were suspended in 360mL of tetrahydrofuran and 90mL of water, and degassed by passing nitrogen gas through the solution. Under a nitrogen atmosphere, the reaction solution was heated to 80°C and stirred for 12 hours. After cooling to room temperature, 100mL of ethyl acetate was added, and the mixture was extracted with 200mL of water. After concentrating the organic layer, the resulting crude product was purified using a silica gel column (heptane-ethyl acetate) to obtain 6.4g of compound S-34 (yield 59%).

[0472] The NMR measurement data for compound S-34 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120°C and stirred under reflux for 1 hour. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layers were concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 5.5 g of compound S-35 (yield 81%).

[0474] The NMR measurement data for compound S-35 was as follows: 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. 2-Isocyanatoethyl acrylate (0.63 g) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, 0.5 g of 2-isocyanatoethyl acrylate was added, and the reaction was continued for another 24 hours. Saturated sodium bicarbonate aqueous solution was added to the reaction solution, followed by 50 mL of chloroform, and the mixture was extracted. 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 1.0 g of compound M-14 (yield 24%).

[0476] The NMR measurement data for compound M-14 was as follows: 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 using the following synthesis method.

[0478] [ka]

[0479] 6.7 g of ortho-vanillin and 5.0 g of 2-aminobenzenethiol were dissolved in 10 mL of ethanol. The reaction mixture was heated under reflux and stirred for 5 hours. After cooling to room temperature, it was stirred at room temperature under air for 48 hours. After concentrating the reaction mixture, the resulting solid was filtered off, washed with 2-butanone, and dried under reduced pressure to obtain 5.4 g of compound S-36 (yield 53%).

[0480] The NMR measurement data for compound S-36 was as follows: 1 H 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, and extraction was performed. After concentrating the organic layer, the resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 2.9 g of compound S-37 (yield 59%).

[0482] The NMR measurement data for compound S-37 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120 °C and stirred under reflux for 3 hours. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layer was concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 3.5 g of compound S-38 (yield 94%).

[0484] The NMR measurement data for compound S-38 was as follows: 1 H 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. 2-isocyanatoethyl acrylate (0.65 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 1.3 g of compound M-15 (yield 32%).

[0486] The NMR measurement data for compound M-15 was as follows: 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 using the following synthesis method.

[0488] [ka]

[0489] 3.7 g of 5-bromovanillin and 2.0 g of 2-aminobenzenethiol were dissolved in 10 mL of ethanol. The reaction mixture was heated under reflux and stirred for 5 hours. After cooling to room temperature, it was stirred at room temperature under air for 72 hours. After concentrating the reaction mixture, the resulting solid was filtered off, washed with 2-butanone, and dried under reduced pressure to obtain 3.5 g of compound S-39 (yield 65%).

[0490] The NMR measurement data for compound S-39 was as follows: 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 (3.3g), bis(bromomethyl)oxetane (1.2g), and potassium carbonate (1.4g) were dissolved in 10mL 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. After concentrating the organic layer, 3.7g of the crude product of compound S-40 was obtained.

[0492] The NMR measurement data for compound S-40 was as follows: 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 (3.7g), dibenzothiophene-4-boronic acid (2.5g), and potassium phosphate (3.2g) were suspended in 60mL of dioxane and 10mL of water, and degassed by passing nitrogen gas through the solution. 81mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it 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 resulting organic layer and stirred for 30 minutes. After Celite filtration, the solution was concentrated, and the resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 4.7g of crude compound S-41.

[0494] The NMR measurement data for compound S-41 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 120 °C and stirred under reflux for 3 hours. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layer was concentrated. The resulting crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 5.5 g of compound S-42.

[0496] The NMR measurement data for compound S-42 was as follows: 1H 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. 2-isocyanatoethyl acrylate (0.83 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 2.8 g of compound M-16 (45% yield).

[0498] The NMR measurement data for compound M-16 was as follows: 1 H 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 using the following synthesis method.

[0500] [ka]

[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, and extraction was performed. After concentrating the organic layer, the resulting crude product was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 1.9 g of compound S-43 (79% yield).

[0502] The NMR measurement data for compound S-43 was as follows: 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 passing nitrogen gas through the solution. 181 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the resulting organic layer and stirred for 30 minutes. After Celite filtration, the solution was concentrated, and the resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 15 g of crude compound S-44.

[0504] The NMR measurement data for compound S-44 was as follows: 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] Crude compound S-44 (5.0 g), 2-mercaptobenzothiazole (0.90 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 70 mL of toluene. Under a nitrogen atmosphere, the reaction solution was heated to 120 °C and stirred under reflux for 2 hours. After the mixture cooled to room temperature, 20 mL of tetrahydrofuran was added to make a homogeneous solution, and it was washed with 1 M aqueous sodium hydroxide solution. Subsequently, it was washed with 0.1 N hydrochloric acid and water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated. The obtained crude product was dissolved in 20 mL of dichloromethane and slowly added dropwise to 150 mL of acetonitrile with stirring. After stirring for a further 2 hours, the precipitate was filtered off. The obtained solid was again dissolved in 80 mL of dichloromethane, passed through a silica gel short-pass column, and concentrated to obtain 3.8 g of compound S-45 (yield 73%).

[0506] The NMR measurement data for compound S-45 was as follows: 1 H 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. 2-Isocyanatoethyl acrylate (0.68 g) 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 resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 3.0 g of compound M-17 (80% yield).

[0508] The NMR measurement data for compound M-17 was as follows: 1H 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 using the following synthesis method.

[0510] [ka]

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

[0512] The NMR measurement data for compound S-46 was as follows: 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. 2-isocyanatoethyl acrylate (0.60 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 1.3 g of compound M-18 (yield 36%).

[0514] The NMR measurement data for compound M-18 was as follows: 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 using the following synthesis method.

[0516] [ka]

[0517] 3,6-Dibromo-9H-carbazole (10 g), dibenzothiophene-4-boronic acid (14.7 g), and potassium phosphate (19.6 g) were suspended in 100 mL of toluene, 100 mL of ethanol, and 50 mL of water, and degassed by passing nitrogen gas through the solution. 11 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated 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 of compound S-47 (yield 92%).

[0518] The NMR measurement data for compound S-47 was as follows: 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 (diglyme). The reaction mixture was heated to 150°C and stirred for 3 hours. After cooling to room temperature, the resulting solid was filtered off and washed with acetone to obtain 3.3 g of compound S-48 (70% yield).

[0520] The NMR measurement data for compound S-48 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 150°C and stirred under reflux for 2 hours. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layer was concentrated. The resulting crude product was purified by silica gel column (hexane·ethyl acetate) to obtain 0.92 g of compound S-49 (yield 83%).

[0522] The NMR measurement data for compound S-49 was as follows: 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. 2-isocyanatoethyl acrylate (0.37 g) was added to this solution, and the reaction was carried out at room temperature. After 72 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 1.3 g of compound M-19 (yield 53%).

[0524] The NMR measurement data for compound M-19 was as follows: 1H 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 using the following synthesis method.

[0526] [ka]

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

[0528] The NMR measurement data for compound S-50 was as follows: 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. 2-isocyanatoethyl acrylate (0.82 g) was added to this solution, and the reaction was carried out at room temperature. After 72 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 1.3 g of compound M-20 (yield 36%).

[0530] The NMR measurement data for compound M-20 was as follows: 1 H 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 using the following synthesis method.

[0532] [ka]

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

[0534] The NMR measurement data for compound S-51 was as follows: 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. 2-isocyanatoethyl acrylate (0.93 g) was added to this solution, and the reaction was carried out at room temperature. After 72 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 1.9 g of compound M-21 (yield 37%).

[0536] The NMR measurement data for compound M-21 was as follows: 1H 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 using the following synthesis method.

[0538] [ka]

[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 (diglyme). The reaction mixture was heated to 120°C and stirred for 3 hours. After cooling to room temperature, the resulting white solid was filtered off, washed with methanol, and dried under reduced pressure to obtain 1.6 g of compound S-52 (yield 53%).

[0540] The NMR measurement data for compound S-52 was as follows: 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. Under a nitrogen atmosphere, the reaction solution was heated to 100°C and stirred for 5 minutes. After the mixture cooled to room temperature, it was extracted with ethyl acetate and washed with 1 M sodium hydroxide aqueous solution. The aqueous layer was re-extracted with ethyl acetate, and the combined organic layer was concentrated. The resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 0.9 g of compound S-53 (yield 71%).

[0542] The NMR measurement data for compound S-53 was as follows: 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. 2-isocyanatoethyl acrylate (0.5 g) was added to this solution, and the reaction was carried out at room temperature. After 48 hours, saturated sodium bicarbonate aqueous solution 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 using a silica gel column (hexane-ethyl acetate) to obtain 1.1 g of compound M-22 (yield 55%).

[0544] The NMR measurement data for compound M-22 was as follows: 1H 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 using the following synthesis method.

[0546] [ka]

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

[0548] The NMR measurement data for compound S-54 was as follows: 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 passing nitrogen gas through the solution. 62 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through for another 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred under reflux for 2 hours. After cooling to room temperature, it 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 over anhydrous magnesium sulfate. This solution was concentrated, and the resulting crude product was purified by silica gel column (dichloromethane, ethyl acetate) to obtain 2.5 g of compound S-55 (yield 75%).

[0550] The NMR measurement data for compound S-55 was as follows: 1 H 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. To this solution, 0.51 g of 2-isocyanatoethyl acrylate was added, and the mixture was reacted at room temperature for approximately 150 hours. After the reaction was complete, the mixture was purified using a silica gel column (dichloromethane, ethyl acetate), and the resulting fraction was concentrated to a total volume of 13 g at a temperature below 30°C. This solution was added dropwise to 160 mL of ice-cold methanol and stirred for 2 hours. The precipitate was filtered off, washed with methanol, and dried to obtain 1.9 g of compound M-23 (yield 71%).

[0552] The NMR measurement data for compound M-23 was as follows: 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 using the following synthesis method.

[0554] [ka]

[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 and stirred for 5 hours while monitoring the reaction by LC analysis. After adding water to the reaction solution, 100 mL of ethyl acetate was added, 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 using a silica gel column (hexane-ethyl acetate) to obtain 10 g of compound S-56 (yield 49%).

[0556] The NMR measurement data for compound S-56 was as follows: 1H 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. To this solution, 2.55 g of 2-isocyanatoethyl acrylate (Showa Denko K.K., Karenz AOI) was added, and the reaction was carried out at room temperature. After 24 hours, 0.4 g of 2-isocyanatoethyl 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 it was concentrated to approximately 50 mL. After removing insoluble matter, the mixture was concentrated, and the resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 7.6 g of compound M-24 (yield 58%).

[0558] The NMR measurement data for compound M-24 was as follows: 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-24 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0560] (Comparative Example 2) Compound M-25 was prepared using the following synthesis method.

[0561] [ka]

[0562] 13.60 g of 2-bromobenzenethiol, 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 stirred for 4 hours while monitoring the reaction by LC analysis. 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 Glauber's salt and concentrated. The crude product obtained by concentration was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 13.2 g of compound S-57 (yield 93%).

[0563] The NMR measurement data for compound S-57 was as follows: 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-boronic acid (3.5 g), and potassium carbonate (2.5 g) were suspended in 20 mL of THF and 2.0 mL of water, and degassed by passing nitrogen gas through the solution. 30 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the resulting organic layer and stirred for 30 minutes. After Celite filtration, the solution was concentrated, and the resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 2.9 g of compound S-58 (yield 98%).

[0565] The NMR measurement data for compound S-58 was as follows: 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 2-isocyanatoethyl acrylate (Showa Denko K.K., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, 500 mg of 2-isocyanatoethyl acrylate was added, and the reaction was carried out for another 24 hours. After adding water to the reaction solution, 50 mL of ethyl acetate was added, and the organic layer was extracted. The obtained organic layer was extracted twice with 30 mL of water, and the resulting aqueous layer was back-extracted twice with 50 mL of ethyl acetate. The obtained organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silica gel column (hexane-ethyl acetate) to obtain 1.5 g of compound M-25 (yield 45%).

[0567] The NMR measurement data for compound M-25 was as follows: 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-25 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0569] (Comparative Example 3) Compound M-26 was prepared using the following synthesis method.

[0570] [ka]

[0571] Compound S-57 (2.0 g), thianthrene-1-boronic acid (2.7 g), and potassium carbonate (2.5 g) obtained in Comparative Example 2 were suspended in 20 mL of THF and 2.0 mL of water, and degassed by passing nitrogen gas through the solution. 30 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the resulting organic layer and stirred for 30 minutes. After Celite filtration, the solution was concentrated, and the resulting crude product was purified using a silica gel column (hexane-ethyl acetate) to obtain 2.2 g of compound S-59 (yield 68%).

[0572] The NMR measurement data for compound S-59 was as follows: 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-isocyanatoethyl acrylate (Showa Denko K.K., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, 300 mg of 2-isocyanatoethyl acrylate was added, and the reaction was carried out for another 24 hours. After adding water to the reaction solution, 50 mL of ethyl acetate was added, and the organic layer was extracted. The obtained organic layer was extracted twice with 30 mL of water, and the resulting aqueous layer was back-extracted twice with 50 mL of ethyl acetate. The obtained organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silica gel column (hexane-ethyl acetate) to obtain 600 mg of compound M-26 (yield 50%).

[0574] The NMR measurement data for compound M-26 was as follows: 1 H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-26 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0576] (Comparative Example 4) Compound M-27 was prepared using the following synthesis method.

[0577] [ka]

[0578] 4.80 g of 3-bromobenzenethiol, 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 stirred for 4 hours while monitoring the reaction by LC analysis. 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 Glauber's salt and concentrated. The crude product obtained by concentration was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 5.0 g of compound S-60 (100% yield).

[0579] The NMR measurement data for compound S-60 was as follows: 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 (2.3g), dibenzothiophene-4-boronic acid (3.2g), and potassium carbonate (2.9g) were suspended in 23mL of THF and 3mL of water, and degassed by passing nitrogen gas through the solution. 70mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through 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, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.5g of activated carbon was added to the resulting organic layer and stirred for 30 minutes. After Celite filtration, the solution was concentrated, and the resulting crude product was purified by silica gel column (hexane-ethyl acetate) to obtain 2.9g of compound S-61 (yield 87%).

[0581] The NMR measurement data for compound S-61 was as follows: 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-isocyanatoethyl acrylate (Showa Denko K.K., Karenz AOI) was added to this solution, and the reaction was carried out at room temperature. After 24 hours, 400 mg of 2-isocyanatoethyl acrylate was added, and the reaction was carried out for another 24 hours. After adding water to the reaction solution, 100 mL of ethyl acetate was added, and the organic layer was extracted. The obtained organic layer was extracted twice with 50 mL of water, and the resulting aqueous layer was back-extracted twice with 50 mL of ethyl acetate. The obtained organic layer was dried over magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by concentration was purified using a silica gel column (hexane-ethyl acetate) to obtain 1.1 g of compound M-27 (yield 33%).

[0583] The NMR measurement data for compound M-27 was as follows: 1 H 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] A holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-27 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0585] [Table 1]

[0586] In preparing the holographic recording media, the molar concentrations of polymerizable monomers, photopolymerization initiators, and additives were set to specific values, and holographic recording media were prepared and evaluated by changing only the type of polymerizable monomer (Table 1). As shown in Table 1, in Comparative Examples 1 to 4, where the polymerizable monomer used had three hypertropic sites of the same structure, the haze % / totalΔn was 3.6 or higher. In contrast, in Examples 1 to 11, where polymerizable monomers were used in which one of the hypertropic sites was replaced with a different structure, the haze % / totalΔn decreased to 3.5 or lower, resulting in holographic recording media with low haze for equivalent totalΔn.

[0587] In optical element applications for AR glasses light guides, a higher totalΔn of the hologram recording medium allows for brighter projected images and a wider viewing angle. Furthermore, in memory applications, improving totalΔn increases recording capacity. On the other hand, hologram recording media with high haze, particularly in AR glasses wave guide applications, scatter guided light, reducing light utilization efficiency and aesthetics. Therefore, by using the compound of the present invention, which achieves both high totalΔn and low haze, it becomes possible to create AR glasses light guides with excellent light utilization efficiency and aesthetics. Based on the above, it can be said that the compound of the present invention used in the examples is superior to the compound of the comparative example.

[0588] [Refractive index] The refractive indices of the polymerizable monomers produced in the examples and comparative examples were measured by the following method. The results are shown in Table 2. The sample was dissolved in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate in a mass ratio of 4:1 to prepare a test solution at the specified concentration. Two 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 Carnew precision refractometer (Shimadzu Corporation, product name: KPR-2000). The temperature of the test solution was 23°C, and the measurement wavelength was the helium lamp d line (587.6 nm). Based on the measurement results, a calibration curve showing the correlation between sample concentration and refractive index was created, and the refractive index at a sample concentration of 100% by mass was determined from the obtained calibration curve and was defined as the refractive index of the sample.

[0589] [Table 2]

[0590] Table 2 shows that the refractive index of all the compounds in the examples is 1.65 or higher, indicating that all of these compounds have a sufficient refractive index to be used as high refractive index monomers. Table 1 shows that the hologram medium containing the compound of the example has a total Δn equivalent to or better than that of the hologram medium containing the compound of the comparative example. Therefore, the compound of the example has improved compatibility with the medium while maintaining hologram recording performance, and is superior to the compound of the comparative example.

[0591] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications are possible without departing from the intent and scope of the invention. This application is based on Japanese Patent Application No. 2021-49181, filed on 23 March 2021, which is incorporated herein by reference in its entirety. [Explanation of Symbols]

[0592] S Hologram Recording Medium M1, M2, M3 mirrors L1 Semiconductor laser light source for recording light L2 Laser light source for regenerative light PD1, PD2, PD3 Photodetector PBS Polarizing Beam Splitter 1 LED unit

Claims

1. A compound represented by the following formula (1). 【Chemistry 1】 [In the formula, A represents a (meth)acryloyl group. L represents a branched (n+1) valent linking group. R １ R represents an aromatic ring group which may have substituents. ２ R represents a monovalent organic group which may have substituents. However, R1 represents a sulfur-containing aromatic heterocyclic group which may have substituents, or an aromatic ring group which has a sulfur-containing aromatic heterocyclic group as a substituent, and / or R2 has a benzothiazole ring. １ , X ２ Each of these independently represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have 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. Furthermore, the number of (meth)acryloyl groups in the formula is 1. In the formula, two R １ These elements may be joined to each other at arbitrary positions to form a ring structure. Provided that in the formula, R １ = R ２ , X １ = X ２ , and p=1 are not all satisfied at the same time.]]

2. The aforementioned R ２ The compound according to claim 1, wherein the compound has a substructure represented by the following formula (2). 【Chemistry 2】 [In the formula, J represents an optionally substituted carbon atom or an optionally substituted nitrogen atom, and G represents a sulfur atom, an oxygen atom, or an optionally substituted nitrogen atom.]

3. A compound represented by the following formula (3). 【Transformation 3】 [In the formula, R １ R represents an aromatic ring group which may have substituents. ２ R represents a monovalent organic group which may have substituents. １ R represents a sulfur-containing aromatic heterocyclic group which may have substituents, or an aromatic ring group which has a sulfur-containing aromatic heterocyclic group as a substituent, and / or R ２ It has a benzothiazole ring. X １ , X ２ Each of these independently represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. p represents an integer of 0 or 1. In the formula, two R １ These elements may be joined to each other at arbitrary positions to form a ring structure. However, in the formula, R １ = R ２ , X １ = X ２ It is not possible for all of these conditions to hold true simultaneously.

4. A method for producing the compound according to claim 3, characterized by performing a ring-opening reaction on an aliphatic cyclic compound represented by the following formula (4). 【Chemistry 4】 [In the formula, R １ X represents an aromatic ring group which may have substituents. １ represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. p represents an integer of 0 or 1. Z represents an aliphatic linking group which may have substituents and may be branched. r represents an integer of 0 or 1. In the formula, two R １ These elements may be joined to each other at any position to form a ring structure.

5. A method for producing the compound according to claim 4, wherein the aliphatic cyclic compound represented by formula (4) is a compound represented by the following formula (5) or formula (6). 【Transformation 5】 [In the formula, R １ X represents an aromatic ring group which may have substituents. １ represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have substituents. p represents an integer of 0 or 1. In the formula, two R １ These elements may be joined to each other at any position to form a ring structure.

6. A polymerizable composition containing the compound described in claim 1 or 2 and a polymerization initiator.

7. A holographic recording medium comprising the polymerizable composition according to claim 6.

8. A polymer obtained by polymerizing the polymerizable composition described in claim 6.

9. An optical material comprising the polymer described in claim 8.

10. An optical component comprising the polymer described in claim 8.

11. A high-capacity memory including the hologram recording medium described in claim 7.

12. An optical element obtained by recording a hologram on a holographic recording medium as described in claim 7.

13. AR glasses comprising the optical element described in claim 12.

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